KR101537459B1 - Silica-loaded catalyst - Google Patents

Abstract

A silica-supported catalyst for use in producing a corresponding unsaturated nitrile by vapor phase catalytic ammoxidation of propane or isobutane, which comprises a metal oxide represented by the following formula (1) and having an average pore diameter of 60 to 120 nm A total pore volume of 0.15 cm 3 / g or more, a specific surface area of 5 to 25 m 2 / g, and a crystallite size of 40 to 250 nm, which is determined from the half value width of the (001) peak by X-ray diffraction.
MoV _a Nb _b X _c T _d Z _e O _n (1)
(In the formula (1), X represents at least one or more elements selected from Sb and Te, T represents at least one or more elements selected from Ti, W, Mn and Bi, and Z represents La, Ce, Yb And Y, wherein a, b, c, d, e, and n each represent an integer of from 0.05 to 0.5, 0.01 to 0.5, 0.001 to 0.5, 0 ≤ e ≤ 1, and n is a value satisfying the balance of valence).

Description

Silica-supported catalyst {SILICA-LOADED CATALYST}

The present invention relates to a silica-supported catalyst used in the production of unsaturated nitriles.

Conventionally, a method of producing a corresponding unsaturated carboxylic acid or unsaturated nitrile by gas phase catalytic oxidation or gas phase contact ammoxidation of propylene or isobutylene is well known, but recently, propane or isobutane was replaced by a vapor phase A method of producing a corresponding unsaturated carboxylic acid or unsaturated nitrile by catalytic oxidation or gas-phase contact ammoxidation has received attention. Therefore, various oxide catalysts have been proposed as catalysts for gas phase catalytic ammonia oxidation of propane or isobutane.

Patent Document 1 discloses a silica-supported catalyst having a large pore volume by using silica sol and powdered silica as raw materials for silica.

Patent Document 2 discloses a catalyst in which the pore distribution is adjusted to a specific range as a complex oxide catalyst used for producing acrolein and acrylic acid.

Patent Document 3 discloses a particulate porous ammoxidation catalyst in which pores are controlled within a specific range in order to improve the target yield.

Patent Document 1: JP-A-2002-219362 Patent Document 2: JP-A-2003-220334 Patent Document 3: International Publication No. 2004/078344 pamphlet

When the silica sol and the powder silica are mixed as described in Patent Document 1, the pore volume can be increased but the average pore diameter is not increased. Therefore, although the effect of improving the fluidity by increasing the pore volume is seen, the yield of the object can not be improved. Further, there is no description about the combustion of raw ammonia, which is one of the problems in producing nitrile by gas phase catalytic ammonia oxidation of alkane.

Patent Document 2 discloses that the yield is increased by controlling the pore diameter. However, there is a description of tableting molding, and it is considered that the fluidity is insufficient. Therefore, it is known that the catalyst is a catalyst for a fixed bed reaction and is a catalyst unsuitable for fluidized bed reaction.

The method described in Patent Document 3 improves the yield of the object by setting the pore diameter to a specific range. The inventors of the present invention conducted a follow-up experiment according to the method described in the above-mentioned document, and found that the pore distribution of the obtained catalyst was such that the cumulative volume of pores having a pore diameter of 80 angstroms or less was 20% or less with respect to the total pore volume of the catalyst, Of the total pore volume of the catalyst is 20% or less with respect to the total pore volume of the catalyst. &Quot; However, it has become clear that the pore is distributed in a relatively small area between 80 and 1000 angstroms in diameter. In the alkaline oxidation catalyst of alkane having strong oxidizing power, pores having small diameters are inadequate because combustion of the raw material ammonia and / or decomposition reaction of the target are likely to proceed. Further, since the crystallite size is not specified, it is considered that the improvement of the yield is not sufficient.

SUMMARY OF THE INVENTION In view of the above circumstances, it is an object of the present invention to provide a catalyst having a low raw material ammonia burning rate and a high yield of a target product.

Under these circumstances, the inventors of the present invention have conducted intensive studies to solve the above problems of the prior art, and as a result, they have found that a silica support having a composition including at least Mo, V, and Nb and having a specific property value such as an average pore diameter, It has been found that unsaturated nitrile can be efficiently produced because the yield of the objective product can be greatly improved by using the catalyst and further the combustion of raw material ammonia can be suppressed and the present invention has been accomplished.

That is, the present invention is as follows.

[1] A silica-supported catalyst for use in producing a corresponding unsaturated nitrile by gas phase catalytic ammoxidation of propane or isobutane, which comprises a metal oxide represented by the following formula (1) The total pore volume is 0.15 cm 3 / g or more, the specific surface area is 5 to 25 m 2 / g, and the crystallite size of 40 to 250 nm, which is determined from the half-value width of the (001) peak by X-ray diffraction, Supported catalyst.

MoV _a Nb _b X _c T _d Z _e O _n (1)

(In the formula (1), X represents at least one or more elements selected from Sb and Te, T represents at least one or more elements selected from Ti, W, Mn and Bi, and Z represents La, Ce, Yb And Y. a, b, c, d and e each represent an integer of 0.05? A? 0.5, 0.01? B? 0.5, 0.001? C? 0.5, 0? D? e ≤ 1, and n is a value satisfying the balance of valence valencies)

[2] The method according to the above [1], wherein the pore volume of the pores having a pore diameter of less than 60 nm is less than 30% of the total pore volume and the pore volume of the pore having a pore diameter of more than 120 nm is less than 30% ≪ / RTI >

[3] The silica-supported catalyst according to [1] or [2], wherein the amount of silica to be supported is 20 to 70 mass% with respect to the total mass of the catalyst composed of the metal oxide and silica.

[4] A method for producing a silica-supported catalyst, comprising the following steps (I) to (IV);

(I) an atomic ratio a of V, a atomic ratio b of Nb, an atomic ratio c of X, an atomic ratio d of T, and a circle of Z containing Mo, V, Nb, X, T and Z, Wherein the molar ratio e is 0.05? A? 0.5, 0.01? B? 0.5, 0.001? C? 0.5, 0? D? 1 and 0? E?

(II) a step of drying the raw material combination solution to obtain a dry powder,

(III) a step of shearing the dried powder at 200 to 400 캜 to obtain a shear fired body,

(IV) a step of preliminarily firing the shear fired body at 600 to 750 ° C to obtain a fired body

(I) having an average primary particle diameter of from 3 to less than 20 nm with respect to the total mass of the silica raw material, from 30 to 70% by mass of the total mass of the silica raw material, (Ii) a silica sol having an average primary particle diameter of 20 to 100 nm in mass%, a silica sol having an average primary particle diameter of 50 nm or less in an amount of 30 to 70 mass% based on the total mass of the silica raw material, i), the silica sol (ii) and the powder silica is 100% by mass based on the silica.

[5] A process for producing a corresponding unsaturated nitrile by subjecting propane or isobutane to gas-phase contact ammoxidation reaction using the silica-supported catalyst described in any one of [1] to [3] above.

According to the present invention, it is possible to provide a catalyst having a low ammonia burning rate and a high yield of a desired product.

Hereinafter, a mode for carrying out the present invention (hereinafter referred to as " present embodiment ") will be described in detail. On the other hand, the present invention is not limited to the following embodiments, but various modifications can be made within the scope of the present invention.

The silica-supported catalyst of this embodiment,

A silica-supported catalyst for use in producing a corresponding unsaturated nitrile by gas phase catalytic ammoxidation of propane or isobutane,

MoV _a Nb _b X _c T _d Z _e O _n (1)

(In the formula (1), X represents at least one or more elements selected from Sb and Te, T represents at least one or more elements selected from Ti, W, Mn and Bi, and Z represents La, Ce, Yb And Y, wherein a, b, c, d, e, and n each represent an integer of from 0.05 to 0.5, 0.01 to 0.5, 0.001 to 0.5, 0 < / = e < / = 1, and n is a value satisfying the valence balance), and the average pore diameter is 60 to 120 nm, the total pore volume is 0.15 cm & Further, the specific surface area is 5 to 25 m 2 / g, and the crystallite size determined from the half value width of the (001) peak by X-ray diffraction is 40 to 250 nm.

The silica-supported catalyst of the present embodiment has a good catalytic performance because the metal composition ratio of the metal oxide contained in the catalyst is optimized. The method for producing the silica-supported catalyst of the present embodiment is not particularly limited, but it is preferable to produce it by a method including the following steps (I) to (IV).

(I) an atomic ratio a of V, a atomic ratio b of Nb, an atomic ratio c of X, an atomic ratio d of T, a circle of Z A process for preparing a raw material combination solution having a boiling point e of 0.05? A? 0.5, 0.01? B? 0.5, 0.001? C? 0.5, 0? D?

(II) a step of drying the raw material combination solution to obtain a dry powder,

(III) a step of shearing the dried powder at 200 to 400 캜 to obtain a shear fired body,

(IV) a step of preliminarily firing the shear fired body at 600 to 750 ° C to obtain a fired body

(I) having an average primary particle diameter of from 3 to less than 20 nm with respect to the total mass of the silica raw material, from 30 to 70% by mass of the total mass of the silica raw material, (Ii) a silica sol having an average primary particle diameter of 20 to 100 nm in mass%, a silica sol having an average primary particle diameter of 50 nm or less in an amount of 30 to 70 mass% based on the total mass of the silica raw material, i), the silica sol (ii) and the powder silica is 100% by mass based on the silica.

(Process (I) raw material combination process)

The process (I) contains Mo, V, Nb, X, T and Z, and has an atomic ratio a of V, a atomic ratio b of Nb, an atomic ratio c of X, Wherein the atomic ratio e of the raw material mixture solution is 0.05? A? 0.5, 0.01 b? 0.5, 0.001? C? 0.5, 0? D?

In the raw material combination step, the constituent elements of the silica-supported catalyst are dissolved or dispersed in a solvent and / or a dispersion medium at a specified ratio to obtain a raw material combination solution. As the solvent of the raw material combination liquid, usually water can be used. Wherein the raw material combination liquid contains at least one element selected from the group consisting of Mo, V, Nb, X, T and Z (X is at least one or more elements selected from Sb and Te, T is at least one or more elements selected from Ti, And Z is at least one element selected from La, Ce, Yb and Y). As the raw material of the raw material combination liquid, a salt or a compound containing constituent elements of the silica-supported catalyst may be used.

Examples of the raw materials of Mo include ammonium heptamolybdate [(NH ₄ ) ₆ Mo ₇ O ₂₄ .4H ₂ O], molybdenum trioxide [MoO ₃ ], molybdic acid [H ₃ PMo ₁₂ O ₄₀ ], silicomolybdic acid [H ₄ SiMo ₁₂ O ₄₀ ], and molten molybdenum [MoCl ₅ ]. Of these, ammonium heptamolybdate [(NH ₄ ) ₆ Mo ₇ O ₂₄ .4H ₂ O] is particularly preferred.

Raw material for V as the example metavanadate ammonium [NH ₄ VO _3], vanadium pentoxide, [V ₂ O _5], can be used, and vanadium chloride [VCl _4, VCl _3], specifically metavanadate ammonium [NH ₄ VO ₃ ] is preferable.

As the raw material of Nb, for example, niobic acid, an inorganic acid salt of niobium and an organic acid salt of niobium may be used, and niobic acid is particularly preferable. Niobic acid is represented by Nb ₂ O ₅ .nH ₂ O and is also called niobium hydroxide or niobium oxide hydrate. Further, it is preferable to use it as a raw material liquid of Nb having a molar ratio of dicarboxylic acid / niobium of 1 to 4, and as the dicarboxylic acid at this time, oxalic acid is preferable.

The raw material of X (Sb, Te) is not particularly limited as long as it is a material containing these elements, and a compound containing these elements or a metal of these elements solubilized with an appropriate reagent can be used. As the compound containing these elements, an ammonium salt, a nitrate, a carboxylate, a carboxylic acid ammonium salt, a peroxocarboxylate salt, an ammonium peroxocarboxylate salt, a halogenated ammonium salt, a halide, an acetylacetonate, an alkoxide And water-soluble raw materials such as nitrates and carboxylates are preferably used.

The raw material of T (Ti, W, Mn, Bi) is not particularly limited as long as it is a material containing these elements, and a compound containing these elements and a metal obtained by solubilizing the metal of these elements as a suitable reagent can be used. As the compound containing these elements, an ammonium salt, a nitrate, a carboxylate, a carboxylic acid ammonium salt, a peroxocarboxylate salt, an ammonium peroxocarboxylate salt, a halogenated ammonium salt, a halide, an acetylacetonate, an alkoxide And water-soluble raw materials such as nitrates and carboxylates are preferably used.

The raw material of Z (La, Ce, Yb, Y) is not particularly limited as long as it is a material containing these elements, and a compound containing these elements and a metal of these elements solubilized with a suitable reagent can be used. As the compound containing these elements, an ammonium salt, a nitrate, a carboxylate, a carboxylic acid ammonium salt, a peroxocarboxylate salt, an ammonium peroxocarboxylate salt, a halogenated ammonium salt, a halide, an acetylacetonate, an alkoxide And water-soluble raw materials such as nitrates and carboxylates are preferably used.

In the combination of the raw materials, the melting order, the mixing order or the dispersing order of the raw materials of the catalyst constituent elements are not particularly limited. The raw materials may be dissolved, mixed or dispersed in the same aqueous medium, or the aqueous medium may be mixed after the raw materials are individually dissolved, mixed or dispersed in an aqueous medium. Further, heating and / or stirring may be performed if necessary.

One of the important points in the silica-supported catalyst is that component Z is uniformly distributed in the catalyst particles. Here, the uniformity means that there is no bias in the distribution of the component Z among the catalyst particles. Preferably, more than 80% (mass ratio) of the oxide particles containing the component Z is present in the catalyst particles as fine particles having a particle diameter of 1 占 퐉 or less. Uniformity " is defined as a uniformity, which means that when the cross-section of the catalyst particle is subjected to composition analysis, the dispersion value (value obtained by dividing the standard deviation by the average value) of the signal intensity ratio between the component Z and Si is in the range of 0 to 0.5 . Here, the dispersion value is represented by " Dx ".

For the above composition analysis, general composition analysis methods such as SEM-EDX, XPS, SIMS, and EPMA can be used. Preferably, EPMA can be used. Here, EPMA is a name of an Electron Probe X-ray Microanalyzer (sometimes referred to as "X-ray"), and this analyzer observes a characteristic X-ray obtained by irradiating accelerated electron beams to a substance, It is a device capable of analyzing the composition of a minute domain (spot) which is irradiated with an electron beam. With this EPMA, information on the concentration distribution and compositional change of a specific element can be generally obtained with respect to the cross section of solid particles such as catalyst particles and carrier particles.

On the other hand, the dispersion value (Dx) of the intensity ratio of the component Z and Si by the EPMA can be obtained by the following method according to the EPMA-based surface analysis method of the particle cross section performed in the ordinary catalyst field It is measured and calculated in the following manner. That is, first, the distribution of the X-ray peak intensity (count number ISi) of Si relative to an arbitrary position (x, y) of the cross section of the catalyst particle is measured so as to cover the entire area of the cross section of the catalyst particle. Then, similarly, regarding the component Z, the distribution of the X-ray peak intensity (count number IX) is measured so as to cover the entire area of the catalyst particle cross section. The peak intensity ratio IR (IR = IX / ISi) of the component Z and Si at the same position (x, y) is obtained based on the obtained series of data (x, y, ISi, IX) , A simple average (IR) av and a standard deviation S of IR are obtained. The value obtained by dividing the standard deviation S by the simple average (IR) av is defined as the dispersion value Dx described above. At this time, the simple average and standard deviation may be obtained by a usual method. In the present specification, the term " a silica-supported catalyst (also simply referred to as " catalyst ") includes those obtained by removing the pore-forming material from the sintered body after sintering, The same value is obtained even after the firing process and before the removal process of the gaseous body.

In order to avoid inaccurate data due to the edge effect of the particle cross section in the above measurement, except for the region corresponding to 10% of the cross-sectional area in the cross section of the catalyst particle and corresponding to the particle outer circumferential portion, It is preferable to calculate 90% area data from the center as a valid area. Of course, it is also possible to perform the above surface analysis by EPMA only with respect to the inside of the section of the catalyst particle limiting the area of 10% of the peripheral portion of the particle from the beginning, and obtain the dispersion value Dx from the data.

Since the catalyst in this embodiment is a silica-supported catalyst supported on silica, the raw material combination solution is prepared so as to contain a silica raw material. From the viewpoint that the average pore diameter of the catalyst is controlled to 60 to 120 nm by the silica sol, the raw material combination liquid is preferably silica sol having an average primary particle diameter of 3 nm or more and less than 20 nm in an amount of 0 to 30 mass% with respect to the total mass of the silica raw material (i) a silica sol (ii) having an average primary particle diameter of 20 to 100 nm in an amount of 30 to 70 mass% based on the total mass of the silica raw material, an average primary particle of 30 to 70 mass% based on the total mass of the silica raw material (I), the silica sol (ii) and the powder silica is 100 mass% based on the silica. More preferably 5 to 20% by mass of the silica sol (i), 30 to 60% by mass of the silica sol (ii), and 30 to 50% by mass of the powdered silica. The order of adding these silica raw materials to the raw material combination liquid is not particularly limited and may be mixed before adding the raw material mixture solution. Although the reason is not clear, it has been found by the inventors of the present invention that a catalyst having a large average pore diameter and high abrasion resistance can be produced by using silica sol (i), silica sol (ii) and powdered silica in a specific amount .

When silica sol (i) and silica sol (ii) are used, it is considered that silica particles having a small particle diameter are contained between silica particles having a large particle size, thereby reducing the fine pores of the catalyst. It is believed that addition of the powdered silica prevents the agglomeration of the silica sol to increase the large pores. Since the average pore diameter of the catalyst of the present embodiment is larger than that of the conventional catalyst, it is presumed that the rate of diffusion of the raw material ammonia and the target in the catalyst particle is increased and / or the reaction temperature is made uniform by the diffusion of heat in the catalyst particle. The combustion of the raw material ammonia and the decomposition of the object can be suppressed.

The metal contained as an impurity in the silica raw material sometimes affects the performance of the silica-supported catalyst to be prepared. An example of the impurity of the silica raw material is sodium. The amount of sodium is preferably 0.02 or less, more preferably 0.01 or less, per 100 silicon atoms. When sodium is contained in excess of 0.02 atoms per 100 atoms of silicon, decomposition reaction of the raw material and / or the desired product tends to occur easily when the obtained silica-supported catalyst is used in the ammoxidation reaction.

In the case of producing unsaturated nitrile by gas phase catalytic ammoxidation of an alkane, the reaction of the raw ammonia and the decomposition of the unsaturated nitrile tend to occur because of the reaction in the presence of a catalyst having a strong oxidizing power and / or at a high temperature due to the low reactivity of the alkane . When the raw material ammonia is combusted, ammonia used in the production of the unsaturated nitrile is insufficient and it is necessary to supply a large amount of ammonia to the alkane, so that productivity is lowered. In the present embodiment, unsaturated nitrile can be efficiently produced by suppressing combustion of raw material ammonia. Naturally, the yield is improved by suppressing the decomposition of the target unsaturated nitrile.

When the average pore diameter of the catalyst is less than 60 nm, the combustion of the raw material ammonia and the decomposition of the object tend to occur easily. On the other hand, when the average pore diameter exceeds 120 nm, since the strength of the abrasion resistance becomes small, it becomes a catalyst which is not suitable for the fluidized bed reaction. From the above viewpoint, the average pore diameter of the catalyst in the present embodiment is adjusted in the range of 60 to 120 nm, preferably in the range of 65 to 100 nm.

The present inventors conducted a follow-up experiment on a catalyst used in a conventional ammonia oxidation reaction of olefins such as propylene or isobutylene, wherein the pore volume of pores having a pore diameter of less than 60 nm was not less than 30% of the total pore volume. In the case of the alkoxylation reaction of alkane, it is considered that the combustion of raw material ammonia and / or the decomposition of the target product are likely to occur if the pore volume of pores having a pore diameter of 60 nm or less is 30% or more of the total pore volume, . Therefore, in the case of the alkoxylation reaction of an alkane, a catalyst having relatively large pores and a uniform pore size is preferable. On the other hand, when the pore volume of the pore having a pore diameter of 120 nm or more is less than 30% of the total pore volume, the strength of the abrasion resistance tends to be large and it tends to be easy to use for the fluidized phase reaction. From the above viewpoints, the silica-supported catalyst of the present embodiment is characterized in that the pore volume of the pores having a pore diameter of less than 60 nm is less than 30% of the total pore volume, and the pore volume of the pores having a pore diameter of more than 120 nm is larger than the total pore volume Is preferably less than 30%.

In order to produce such a catalyst, it is preferable to control the sintering of silica by calcining at 600 to 750 캜 using silica sol having different particle diameters. When calcining at 600 DEG C or higher, the sintering of silica proceeds sufficiently, and the pore volume of the pores having a pore diameter of 60 nm or more increases, which is preferable.

The supported amount of the carrier silica contained in the catalyst is preferably 20% by mass or more from the viewpoint of improving the strength of the catalyst with respect to the total mass of the catalyst composed of the metal oxide and silica, and is preferably 70% by mass or less And more preferably 40 to 65 mass% with respect to the total mass.

The raw material of the silica carrier may be only silica sol, but it is also possible to replace part of the silica carrier with powder silica. By using powdered silica as a raw material for the silica carrier, effects such as improvement of catalytic activity and / or yield of the object can be expected. On the other hand, when the catalyst is prepared only from powdered silica without using silica sol, abrasion resistance of the catalyst is remarkably lowered. In the present embodiment, the term " powdery silica " refers to fine particles of solid SiO ₂ . If the primary particle size of the silica is too large, the obtained catalyst tends to become fragile, so that powdery silica of nanometer size is preferable. The powdery silica is preferably produced by a high-temperature method.

From the viewpoint of easy addition and mixing to the raw material combination liquid, it is preferable to disperse the powdered silica in advance in water. A method of dispersing the powdered silica in water is not particularly limited, and a general homogenizer, a homomixer, an ultrasonic vibrator or the like can be dispersed singly or in combination. The primary shape of the powdered silica at this time may be spherical or spherical.

The average primary particle diameter of the silica sol and the powder silica as the carrier raw materials can be determined by the BET method (BET adsorption isotherm). Generally available silica is believed to have a certain distribution width around the average primary particle diameter. In order to sufficiently exert the ammonia combustion suppressing effect, the smaller the standard deviation in the particle diameter distribution of each silica is, the more preferable. Specifically, the standard deviation is preferably 30% or less of the average primary particle diameter.

In order to control the average pore diameter of the catalyst, it is effective to change the average primary particle diameter of the silica sol. Generally, when the average primary particle diameter of the silica sol is increased, the strength of the resulting catalyst tends to decrease. On the other hand, since an industrial fluidized bed catalyst is preferable to have high strength, silica sol having an average primary particle diameter of 10 nm is generally used as a silica raw material in the past. When the catalyst is prepared by the conventional method using such a silica sol, the average pore diameter is about 20 to 50 nm, the average pore diameter defined in the present embodiment does not satisfy the range of 60 to 120 nm, not. The average pore diameter can be controlled by changing the firing conditions. If the firing temperature is increased and / or the firing time is increased, the average pore diameter tends to become larger. However, when the average pore diameter is controlled by changing the firing conditions, the specific surface area and / or the crystallite size also change, and it is difficult to control the average pore diameter, specific surface area and crystallite size only under the firing conditions. As described above, it is practically impossible to obtain a catalyst satisfying the average pore diameter, specific surface area and / or crystallite size in the catalyst production method described in the background art document. Controlling the average pore diameter by a method using silica sol having different average primary particle diameters is preferable because the specific surface area and / or crystallite size can be controlled according to the firing conditions. The specific surface area and the crystallite size can be controlled by controlling the firing conditions because the temperature range in which the sintering of the silica proceeds and the temperature range in which the crystal grows have a large effect on the specific surface area.

The means for controlling the average pore diameter of the catalyst of the present embodiment to an appropriate range is not particularly limited, and any means can be used as far as the average pore diameter can be controlled within an appropriate range. As a method for controlling the average pore diameter of the catalyst, there are a method of changing the average primary particle diameter of the silica sol as the above-mentioned silica raw material, a method of using powder silica as a part of the silica raw material, a method of controlling the ratio of the silica carrier to the metal oxide And a method of changing the state of the apparatus.

It is preferable that the raw material combination liquid contains powdery silica having an average primary particle diameter of 50 nm or less as a part of the silica raw material in an amount of 30 to 70 mass% based on silica. On the other hand, in the present embodiment, " silica standard " refers to a ratio of the total amount of silica sol and powder silica. It is more preferable that the average diameter of the primary particles of the powdered silica is 10 to 20 nm. Further, the amount of the powdery silica is more preferably 30 to 50 mass% on the basis of silica. The use of powdered silica increases the specific surface area of the catalyst. In order to control the specific surface area and the crystallite size to an appropriate range, the firing temperature is preferably 640 to 750 ° C and the firing time is 1 to 20 hours in the firing, and the average firing rate after completion of the firing is 0.05 to 20 ° C / min It is preferable to calcine.

When controlling the average pore diameter by changing the ratio of the amount of silica supported in the catalyst to the amount of the metal oxide, the amount of silica to be supported is preferably 20 to 70 mass% with respect to the total mass of the catalyst composed of the metal oxide and silica, More preferably, it is in mass%. Generally, when the amount of silica supported is reduced, the surface shifts to the larger diameter side, and the specific surface area becomes smaller. In order to control the specific surface area and the crystallite size to an appropriate range, the sintering temperature of the sintering is calcined at 600 to 700 ° C and the sintering time is 0.1 to 5 hours, and the average temperature decreasing rate after completion of the sintering is 0.5 to 50 ° C / .

As a method of measuring the pore distribution of the catalyst, a gas adsorption method, a mercury intrusion method and the like are known, but the values are different according to the measurement method. The value of the pore distribution of the catalyst in the present embodiment was obtained by mercury porosimetry (Pore Master GT manufactured by QUANTACHROME INSTRUMENTS). Here, the mercury infiltration method is a method in which mercury is injected into the catalyst particles and the distribution of the pore diameter is measured from the relationship between the pressure and the penetration amount at that time. This is because the pore diameter calculated based on the assumption that the shape of the pores is cylindrical Thereby giving an integration curve of the pore volume. The value obtained by firstly differentiating the integrated curve of the pore volume by the pore diameter with respect to the corresponding pore diameter is called a pore distribution. More specifically, 0.4 to 0.6 g of a sample (catalyst) was placed in a dilatometer (expansion system), degassed by a vacuum pump to a pressure of 6.67 Pa or less, mercury was injected into the dilatometer, the dilatometer was loaded in the autoclave, , The pressure is gradually increased to 413 MPa to trace the drop in the mercury level and to measure the pore distribution from the change in pressure and mercury level (the amount of mercury into the catalyst pores).

In the case of the catalyst, the mercury porosimetry method measures pores between several tens of thousands of angstroms to several hundreds of thousands of pores between catalyst particles, so that pores having a diameter of 200 nm or less are added to the accumulation volume. Further, since the lower limit of the measurement of the pore diameter is 6 nm, pores of 6 nm or more are added to the accumulation volume. Therefore, in this embodiment, the integrated volume of pores having a pore diameter of 6 nm or more and 200 nm or less is defined as the total pore volume.

The total pore volume of the catalyst in the present embodiment is at least 0.15 cm 3 / g from the viewpoint of fluidity in the fluidized bed reaction. When the total pore volume is less than 0.15 cm 3 / g, the fluidity is lowered and the yield is lowered due to unevenness in the reaction temperature. The total pore volume tends to be larger the larger the average pore diameter and / or the larger the specific surface area. The means for adjusting the total pore volume may be a method of increasing the average pore diameter using silica sol having different particle diameters or a method of increasing the specific surface area by reducing the firing temperature and / or shortening the firing time in the firing step .

The average pore diameter of the catalyst is calculated using equation (i), assuming that the pores are cylindrical.

D = 4V / S (i)

Here, D: average pore diameter (m), V: total pore volume (m 3 / g), and S: specific surface area (m 2 / g).

Hereinafter, the raw material combining process is described as an example in which a raw material combination solution of a silica-supported catalyst containing an Mo compound, a V compound, an Nb compound, an X compound, a T compound and a Z compound is prepared using a solvent and / Explain.

Mo compound, V compound, X compound and Z compound are added to water and heated to prepare a raw material combination liquid (A). The heating temperature and the heating time at the time of preparing the raw material combination liquid (A) are preferably adjusted so that the raw material compound can be sufficiently dissolved, and the heating temperature is preferably 70 to 100 캜, Is from 30 minutes to 5 hours. The number of revolutions of stirring at the time of heating is adjusted to an appropriate number of revolutions in which the raw material is easily dissolved. When the raw material is a metal salt, from the viewpoint of sufficiently dissolving it, it is preferable to maintain the stirring state. At this time, the inside of the vessel may be an air atmosphere, but it may be a nitrogen atmosphere in view of adjusting the oxidation number of the obtained composite oxide catalyst. The state after the heating of the raw material combination liquid (A) is completed is referred to as a raw material combination liquid (A '). The temperature of the raw material combination solution (A ') is preferably maintained at 20 ° C or more and 80 ° C or less, and more preferably 40 ° C or more and 80 ° C or less. If the temperature of the raw material combination liquid (A ') is less than 20 占 폚, there is a possibility that the metal species dissolved in the raw material combination liquid (A') may be precipitated. After the heating of the raw material combination liquid (A) is completed, silica sol is added as a raw material for the carrier. When two or more types of silica sol having different average primary particle diameters are added, the order of adding these silica sols is not particularly limited, and they may be mixed before adding to the raw material combination solution. The temperature of the raw material combination solution (A ') at the time of adding silica sol is preferably 80 ° C or less. When the silica sol is added at a temperature exceeding 80 캜, the stability of the silica sol is weakened, and there is a possibility that the raw material mixture solution becomes gelled. The timing of addition of the silica sol may be either at the beginning of aging described later, during aging or just before the raw material mixture solution is dried, but it is preferably added at the time of the raw material mixture solution (A ') state. Further, from the viewpoint of adjusting the oxidation number of the metal oxide to be obtained, it is preferable to add an appropriate amount of hydrogen peroxide solution to the raw material combination solution (A ') as needed. The timing of adding the hydrogen peroxide solution may be added to the raw material combination solution (A ') or the raw material combination solution (A') at the time of combining, and it may be added before or after the addition of the silica sol. At this time, from the viewpoint of adjusting the oxidation number of the obtained oxide catalyst to an appropriate range, the amount of the hydrogen peroxide solution to be added is preferably 0.01 to 5, more preferably 0.5 to 3, and still more preferably 0.01 to 5, in terms of H ₂ O ₂ / Sb Lt; / RTI >

It is preferable that the heating temperature and the heating time after the addition of the hydrogen peroxide solution to the raw material combination liquid (A ') are adjusted so that the liquid phase oxidation reaction by the hydrogen peroxide solution can sufficiently proceed, and the heating temperature is preferably 30 [ 70 DEG C, and the heating time is preferably 5 minutes to 4 hours. The number of revolutions of stirring at the time of heating is adjusted to an appropriate number of revolutions in which the liquid phase oxidation reaction by the hydrogen peroxide solution is likely to proceed. From the viewpoint of sufficiently promoting the liquid phase oxidation reaction by the hydrogen peroxide solution, it is preferable to maintain the stirring state during heating. The thus prepared raw material combination solution is referred to as (A ").

Subsequently, the Nb compound and the dicarboxylic acid are heated and stirred in water to prepare a mixed solution (B ₀ ). An example of the dicarboxylic acid is oxalic acid [(COOH) ₂ ]. It is preferable to add hydrogen peroxide solution to the mixed liquid (B ₀ ) to prepare the raw material combined liquid (C). At this time, H ₂ O ₂ / Nb (molar ratio) is required to be stabilized in a dissolved state by forming a complex with an Nb compound, to appropriately control the redox state of the constituent elements of the catalyst, , It is preferable to be 0.5 to 20, more preferably 1 to 10.

(A "), the raw material combination liquid (C), the T compound and the powdered silica are suitably mixed in accordance with the intended composition to obtain a raw material combination liquid (D). The obtained raw material combination solution (D) is aged to obtain a raw material combination solution. The powdery silica to be used herein may be added as it is, but it is more preferable to add the powdered silica as an aqueous solution in which water is dispersed in water. At this time, the powdery silica concentration with respect to water is preferably 1 to 30 mass%, more preferably 3 to 20 mass%. When the powder silica concentration is less than 1% by mass, there is a fear that the viscosity of the slurry is too low, so that the shape of the obtained particles is distorted, and recesses are easily formed in the catalyst particles. On the other hand, when the powdery silica concentration exceeds 30 mass%, the viscosity of the raw material mixture solution becomes excessively large, the raw material mixture solution gels and clogging occurs in the pipe, making it difficult to obtain a dry powder, There is a concern.

Aging of the raw material combination liquid (D) means that the raw material combination liquid (D) is left to stand for a predetermined time or stirred. In the case of industrially producing a silica-supported catalyst, there is a case where the processing speed of the spray dryer is controlled so that time is required until spray-drying of a part of the raw material combination solution (D) have. In the meantime, the aging of the mixed solution not subjected to spray drying can be continued. That is, the aging time includes not only the aging time before spray drying but also the time from the start to the end of spray drying.

The silica-supported catalyst is required to sufficiently dissolve and / or disperse the compound containing the catalyst constituent element, to adjust the redox state of the catalyst constituent element appropriately, to obtain the obtained catalyst particle shape and / From the viewpoint of improving the catalytic performance of the resulting composite oxide. The silica sol can be appropriately added. In addition, a part of the silica sol can be used as an aqueous dispersion of powdered silica, and an aqueous dispersion of powdered silica can be appropriately added.

The above-described raw material combining step can be repeatedly performed depending on the production amount.

The raw material combining step in the present embodiment preferably includes the following steps (a) to (d).

(a) preparing a raw material combination solution containing Mo, V, X and component Z

(b) a step of adding silica sol and hydrogen peroxide solution to the raw material combination solution obtained in the step (a)

(c) a step of mixing an aqueous solution containing Nb, a dicarboxylic acid and a hydrogen peroxide solution and a T compound into the solution obtained in the step (b)

(d) a step of adding a powdery silica-containing suspension to the solution obtained in the step (c) and aging the solution.

(Process (II) drying process)

The step (II) is a step of drying the raw material combination solution to obtain a dry powder.

The dry raw material mixture can be obtained by drying the raw material mixture solution in slurry obtained through the raw material combination process. The drying can be carried out by a known method, for example, by spray drying or evaporation drying. In the case of employing the fluidized bed reaction method in the gas-phase contact ammoxidation reaction, it is preferable to employ spray drying because it is preferable to obtain a fine spherical dry powder from the viewpoint of bringing the fluidity into a desired state in the reactor . The atomization in the spray drying method may be a centrifugal method, a two-fluid nozzle method, or a high-pressure nozzle method. As the drying heat source, air heated by steam, an electric heater, or the like can be used. The inlet temperature of the dryer of the spray drying apparatus is preferably 150 to 300 DEG C from the viewpoint of obtaining the desired shape and / or strength of the obtained catalyst particle and improving the catalytic performance of the resultant composite oxide. The outlet temperature of the dryer is preferably 100 to 160 캜.

It is preferable to adjust the spraying speed, the pumping speed of the raw material combination liquid, the number of rotations of the atomizer in the centrifugal system, and the like so that the size of the obtained dry powder becomes suitable. The average particle size of the dry powder is preferably 5 to 200 占 퐉, more preferably 10 to 150 占 퐉.

The average particle size of the dried powder can be obtained by measuring the particle size distribution in accordance with JIS R 1629-1997 " Method of measuring particle size distribution by laser diffraction and scattering method of fine ceramics raw material " More specifically, a part of the dried powder was calcined in the air at 400 DEG C for 1 hour, and the obtained particles were measured using a laser diffraction scattering method particle size distribution measurement apparatus BECKMAN COULTER manufactured by LS230.

The average particle size is measured after a portion of the dried powder is calcined in the air at 400 ° C for one hour in order to prevent the dry powder from dissolving in water. That is, "firing in air at 400 ° C. for one hour" is for measurement only and is not related to the firing process described below. It may be considered that the particle diameter is hardly changed before and after the firing.

More specifically, the average particle size of the dried powder is measured in accordance with the manual attached to the laser diffraction scattering method particle size distribution measuring apparatus (manufactured by BECKMAN COULTER, trade name " LS230 ") as follows. First, after background measurement (RunSpeed 60), 0.2 g of particles are weighed into a screw tube of the appropriate size and 10 cc of water is added. The screw tube is capped (closed) and sufficiently shaken to disperse the particles in water. Ultrasonic waves of 300 W are applied by the apparatus, and the screw tube is sufficiently shaken again. Thereafter, while continuing the application of the ultrasonic waves, the particles dispersed in water are injected into the device body using an eyedropper so as to have an appropriate concentration (concentration 10, PIDS60). When the concentration display is stabilized, the application of the ultrasonic waves is stopped, and the measurement is started after standing for 10 seconds (measurement time: 90 seconds). The value of the median particle diameter of the measurement results is taken as the average particle diameter.

((III) shear firing process and (IV) firing process)

The step (III) is a step of obtaining a shear sintered body by shearing the dried powder at 200 to 400 캜.

Step (IV) is a step of obtaining a sintered body by firing the pre-sintered body at 600 to 750 캜.

In this specification, the step (III) and the step (IV) are collectively referred to as " firing step ".

In the step (III) and the step (IV), the dried powder obtained in the drying step is baked. The conditions such as firing temperature, time, atmosphere and the like are not particularly limited as long as they are appropriately determined in view of the removal of the organic component contained in the dried powder or the crystal growth of the composite oxide. In the manufacturing method of the present embodiment, the conditions such as the temperature are changed as described later, and firing is performed in multiple steps such as shearing and main firing.

In the present specification, the term " pore body " refers to a substance exuded and / or attached to the surface of the sintered body obtained by the main firing described later, and refers to a protruded or attached to the surface of the sintered body. Here, most of the pillar bodies are protruded oxide crystals or other impurities. Particularly, in the case of a sintered body containing a plurality of metals, oxides whose composition is different from that of crystals forming most of the sintered body may be formed in a shape such that the sintered body is exuded from the body portion. In this case, the pillar body is often formed in the form of a plurality of projections (for example, a height of 0.1 mu m to 20 mu m in height) on the surface of the spherical sintered body (for example, 30 to 150 mu m in diameter). The removal of the gaseous body will be described in detail later.

(Firing method of dry powder)

As a firing apparatus for firing the dried powder, for example, a rotary kiln (rotary kiln) can be used. The shape of the firing unit is not particularly limited, but from the viewpoint of continuous firing, it is preferable that the firing unit is a tubular firing tube, and a cylindrical firing unit is particularly preferable. The heating method is preferably an exothermic method in view of easy adjustment of the firing temperature to a desired heating pattern, and an electric furnace can be suitably used. The size and material of the sintered tube may be suitably selected in accordance with the firing conditions and the production amount. The inner diameter of the fired tube is preferably from 70 to 2000 mm, more preferably from 100 to 1200 mm, from the viewpoint that the firing temperature distribution in the catalyst layer does not become uneven and the firing time and production amount are adjusted to appropriate values. In addition, the length of the sintered tube is preferably adjusted to a suitable value, from the viewpoint that the residence time of the dried powder and the catalyst precursor particles in the sintered tube, that is, the distribution of the sintering time, is minimized, the sintering tube is prevented from being distorted, Preferably 200 to 10000 mm, and more preferably 800 to 8000 mm. In the case of impacting the fired tube, the thickness is preferably not less than 2 mm, more preferably not less than 4 mm, from the viewpoint that the thickness thereof is sufficient to prevent breakage by impact. Further, the thickness is preferably 100 mm or less, more preferably 50 mm or less from the viewpoint that the impact is sufficiently transmitted to the inside of the fired tube. The material of the firing unit is not particularly limited as long as it has heat resistance and strength enough not to be broken by impact, and SUS can be suitably used, for example.

In the present specification, the term " catalyst precursor " refers to a compound produced in the course of the calcination step.

In the present firing step, the crystallite size of the catalyst can be controlled. In order to control the crystallite size to an appropriate range, the calcination is preferably carried out at 600 to 750 ° C for 0.1 to 20 hours, more preferably at 650 to 720 ° C for 0.5 to 5 hours. The crystallite size is greatly influenced by the firing temperature and / or time. The crystallite size increases as the firing temperature is increased and / or the firing time is lengthened. The crystal of the silica-supported catalyst is a columnar type, and when the crystal grows in the (001) direction, the aspect ratio to the entire crystal plane is increased. It is known that the ammoxidation reaction proceeds on the upper and lower surfaces and the side surface is the decomposition surface. The crystallite size measured in this embodiment is the length in the (001) direction. If the crystallite size exceeds 250 nm, it is considered that the ratio of the decomposition surface to the entire crystal surface is increased, and the combustion of the raw material ammonia and decomposition of the object do. On the contrary, when the firing temperature is lowered and / or the firing time is shortened, the crystallite size becomes smaller. If the crystallite size is less than 40 nm, the construction of the active sites becomes insufficient, and the combustion of the raw material ammonia and the decomposition of the target product are liable to occur. Therefore, the crystallite size of the catalyst is 40 to 250 nm, preferably 40 to 180 nm. Since the catalyst having a crystallite size in a suitable range has a high degree of crystal completeness and a small ratio of decomposition surfaces to the entire crystal surface, combustion of raw ammonia can be suppressed and an object can be produced with a high yield.

The crystallite size of the catalyst can be obtained by measuring X-ray diffraction, and the (001) peak involved in the reaction overlaps with the impurity peaks that do not participate in the reaction. The pretreatment is carried out by placing 5 to 20 g of the catalyst, 200 ml of water and 2 ml of nitric acid in a pressure vessel and allowing the impurities to dissolve by keeping at 150 to 200 ° C for at least 24 hours under tightly closed conditions. After 24 hours or more, the pressure-resistant container is cooled to room temperature and filtered by a filter paper. The solid obtained by filtration is dried for 24 hours or more in a high-temperature bath set at 30 to 100 DEG C, and X-ray diffraction measurement of the dried powder is carried out to obtain only (001) peak of crystals participating in the reaction.

The crystallite size can be measured by Scherrer's equation from the half-width of the peak obtained by X-ray diffraction after the pretreatment. Specific X-ray measurement conditions were as follows: RIGAKU RINT2500HF / PC, light source: Kα line of Cu, output: 40 kV-20 mA, measurement range (2θ): 5 to 50 °, scan speed: 1 deg / min, Perform 4 circuit measurements. In order to obtain the exact half-value width, it is preferable to correct the enlargement of the half-value width inherent to the apparatus using the standard reference material (LaB6) before the measurement of the sample.

The crystallite size is calculated by the following Scherr's equation (ii) from the half-value width of the (001) peak (plane interval d = 4.02) by X-ray diffraction. (001) peak (surface interval d = 4.02) is a peak derived from crystals involved in the reaction.

L = 0.9? /? Cos? (Ii)

Here, L is the crystallite size (Å), λ is the wavelength (Å), β is the diffraction line width (rad), and θ is the diffraction angle (rad).

The firing atmosphere may be air or air, but it is preferable that at least a part of the firing is carried out while flowing an inert gas substantially free of oxygen such as nitrogen from the viewpoint of adjusting to a preferable redox state. When firing is performed in a batch manner, the amount of the inert gas to be supplied is preferably 50 N / hr or more, more preferably 50 to 5000 N / hr, per 1 kg of the dried powder, And preferably 50 to 3000 N liters / Hr (N liters means liter under standard temperature and pressure conditions, i.e., 0 ° C and 1 atm).

When firing is carried out continuously, the amount of the inert gas to be supplied is preferably 50 N liters or more, preferably 50 N to 5000 N liters, more preferably 50 N liters per kg of dry powder, To 3000 N liters. At this time, the inert gas and the dried powder may be in the form of a counter current or a bundle, but countercurrent contact is preferable in consideration of a gas component generated from the dry powder and an air mixed with the dry powder together with a minute amount.

Dry powders usually contain ammonium roots, organic acids, inorganic acids, etc. in addition to water. When firing while flowing an inert gas substantially free of oxygen, when they evaporate or decompose, the catalyst constituent elements are reduced. In the case where the catalyst constituent element in the dried powder is almost the highest oxidation number, in order to reduce the reduction ratio of the catalyst to a desired range, it is industrially simple because only the reduction is required in the calcination step.

On the other hand, as described later, an oxidizing component or a reducing component may be added to the firing atmosphere so that the reduction ratio of the shear fired body is in a desired range. In the production method of the present embodiment, it is preferable that firing is performed so that the reduction rate of the obtained shear fired body is 8 to 12% and the specific surface area of the catalyst is 5 to 25 m 2 / g. When the specific surface area of the catalyst is 5 to 25 m < 2 > / g, more sufficient activity can be obtained, combustion of raw material ammonia is suppressed, and the yield tends to be further increased. If the specific surface area exceeds 25 m < 2 > / g, the decomposition point of the silica surface increases, and combustion of the raw material ammonia and decomposition of the target tend to occur easily. When the specific surface area is less than 5 m < 2 > / g, sufficient active sites are not formed and the yield tends to decrease. Further, as for the effect of addition of the molybdenum compound for maintaining the yield during the ammoxidation reaction, the effect is more fully exhibited and there is no rapid deterioration, so that the addition amount and the addition frequency of the molybdenum compound tend to be reduced . Although this reason is not clear, it is presumed that if the specific surface area of the catalyst is less than 5 m < 2 > / g, the active surface of the active species involved in the reaction is small and the effect of adding the molybdenum compound is hardly exerted. When the specific surface area of the catalyst is more than 25 m 2 / g, it is presumed that the active surface of the active species becomes large while the molybdenum from the active surface is also rapidly decomposed. Therefore, the specific surface area of the catalyst is 5 to 25 m 2 / g, preferably 8 to 18 m 2 / g. Here, the specific surface area is obtained by the BET 1-point method using Gemini 2360 manufactured by MICROMETRICS.

The reduction ratio of the shear fired body is expressed by the following formula (2)

Reduction rate (%) = ((n ₀ -n) / n ₀ ) × 100 (2)

(Wherein n is the number of oxygen atoms satisfying the valence of constituent elements other than oxygen in the shear-shear body, and n ₀ is the number of oxygen atoms required when constituent elements other than oxygen in the shear- ). ≪ / RTI >

Concretely, the dry powder is calcined under such a condition that the heating temperature of the dried powder starts to rise from a temperature lower than 400 ° C and is continuously or intermittently raised to a temperature within a range of 600 to 750 ° C , Then the firing conditions are adjusted so that the reduction rate of the shear fired body during firing when the heating temperature reaches 400 캜 is 8 to 12%.

The temperature and time at which the catalyst is finally calcined (heated) and the silica content affect the specific surface area of the catalyst. The reduction rate, the calcination temperature and / or the time when the calcination temperature reaches 400 ° C, This is especially significant. When the heating temperature reaches 400 캜, the specific surface area of the catalyst becomes low. When the heating temperature reaches 400 캜, the specific surface area of the catalyst tends to be high when the reduction ratio is high. The firing temperature is 600 ° C. to 750 ° C. for 0.1 to 20 hours. The higher the firing temperature and the longer the time, the smaller the specific surface area of the catalyst. The reason for this is not clear, but in the case of firing in two stages, when the firing temperature is kept constant, the higher the maximum temperature of the shear firing, the larger the specific surface area and the lower the maximum temperature of the shear firing The specific surface area becomes smaller. The temperature lowering rate after firing is preferably 0.05 to 50 占 폚 / min, more preferably 0.05 to 20 占 폚 / min. The specific surface area tends to be reduced when the temperature lowering rate after the main firing is reduced.

The specific surface area and crystallite size of the catalyst can be controlled separately by adjusting the firing conditions. Since the temperature at which the crystal growth progresses is a region of the firing, the crystallite size is controlled by the firing temperature and / or the firing time. Since the temperature range in which the sintering of silica which greatly affects the specific surface area proceeds is wider than the temperature range in which the crystal growth proceeds, it is desirable to control the specific surface area at the temperature decreasing rate after completion of the sintering. Also, since the specific surface area is greatly influenced by the redox degree, it is also preferable to control the reduction rate as an indicator.

In the case of firing with a rotary kiln, it is possible to adjust the specific surface area of the catalyst by adjusting the feed amount of the dry powder at the time of firing. Since the retention time in the system of the dried powder is prolonged by reducing the amount of the feed, the reduction of the dried powder by the reducing gas such as ammonia which is caused by heating the dried powder in the fired tube proceeds, The specific surface area of the catalyst obtained after firing becomes large. On the contrary, when the feed amount is increased, the reduction rate is lowered and the specific surface area of the catalyst becomes smaller. It is also possible to adjust the specific surface area according to the amount of nitrogen at the time of shearing firing. By increasing the nitrogen amount, the component gas for reducing the shear fired powder at the time of firing is quickly discharged out of the system, so that the shear fired body is less likely to be reduced, and as a result, the specific surface area is reduced. Conversely, when the nitrogen content is reduced, the reduction ratio is increased, and the specific surface area of the catalyst is increased.

In order to set the specific surface area of the catalyst to 5 to 25 m < 2 > / g, it is preferable that the reduction ratio when the heating temperature reaches 400 DEG C is set within a range of 8 to 12%, and the final firing temperature is set to 600 to 750 DEG C desirable.

The sintering step is preferably carried out in a temperature range of 200 to 400 캜, and the main sintering is performed in a temperature range of 600 to 750 캜. The preliminary firing and main firing may be performed in succession, or the preliminary firing may be performed once and then firing may be performed again. Further, each of the shearing and main sintering may be divided into several stages.

In the case of measuring the reduction rate of the sintered body under firing, the sample may be taken out of the sintering apparatus at that temperature. However, since the sample may be oxidized by contact with air at high temperature to change the reduction rate, Is taken as a representative sample. As a method for controlling the reduction ratio when the heating temperature reaches 400 캜 in a desired range, specifically, there are a method of changing the shear firing temperature, a method of adding an oxidizing component such as oxygen to the atmosphere at firing, And a method of adding a reducing component to the solution. It is also possible to combine them.

The method of changing the shear firing temperature is a method of changing the reduction ratio when the heating temperature reaches 400 캜 by changing the shear firing temperature. Generally, when the shearing temperature is lowered, the reduction rate is lowered, and when the shearing temperature is increased, the reducing rate tends to increase. Therefore, the reducing rate can be controlled by changing the shearing temperature. It is also possible to control the reduction ratio by increasing or decreasing the amount of nitrogen to be supplied, by increasing or decreasing the amount of dry powder to be fed, or by increasing or decreasing the number of revolutions in firing using a rotary kiln. When the amount of nitrogen to be supplied is increased, the amount of the oxidized component vaporized from the dried powder by the furnace is not oxidized (metal oxide is reduced) by the metal oxide present in the calcining furnace, It is considered that the reduction of the adult body is difficult to proceed. Further, it is considered that, when the dry powder to be supplied is reduced, the reduction time is prolonged by increasing the residence time of the catalyst in the rotary kiln. Further, in the case of a rotary kiln, if the number of revolutions is reduced, the moving speed in the kiln of the catalyst is lowered, so that it is considered that the reduction proceeds because the time for contact with more oxidized components becomes longer.

The reduction ratio of the shear fired body before the completion of the firing is measured by the following formula. Approximately 200 mg of shear bulk is precisely weighed in a beaker. Also, an excess amount of KMnO ₄ aqueous solution having a known concentration is added. Add 150 mL of pure water at 70 ° C, add 2 mL of 1: 1 sulfuric acid (ie, an aqueous sulfuric acid solution obtained by mixing concentrated sulfuric acid and water at a ratio of 1/1), cover the beaker with a watch glass, Deg.] C in a hot water bath, and the sample is oxidized. At this time, KMnO ₄ is excessively present, and unreacted KMnO ₄ is present in the liquid, so that it is confirmed that the liquid color is purple. After completion of the oxidation, the solution is filtered through a filter paper, and the entire amount of the filtrate is recovered. An excess amount of an aqueous sodium oxalate solution whose concentration is known is added to KMnO ₄ present in the filtrate, and the mixture is heated and stirred so that the liquid temperature is 70 ° C. Confirm that the solution becomes colorless and transparent, add 2 mL of 1: 1 sulfuric acid. Stirring is continued while maintaining the liquid temperature at 70 ° C ± 2 ° C, and the solution is titrated with a KMnO ₄ aqueous solution having a known concentration. The end point is where the light color is dimmed by KMnO ₄ and the pink color lasts for about 30 seconds.

The amount of KMnO ₄ consumed in the oxidation of the sample is obtained from the total amount of KMnO ₄ and the total amount of Na ₂ C ₂ O ₄ . Calculating the (n ₀ -n) from the value, and obtains a reduction rate on the basis of this.

The reduction ratio of the sintered body after the completion of the sintering can be measured by the following equation.

In the beaker, 200 mg of mashed material, which is mashed and ground, is identified. 150 mL of pure water at 95 캜, and 4 mL of 1: 1 sulfuric acid (i.e., an aqueous solution of sulfuric acid obtained by mixing concentrated sulfuric acid and water at a ratio of 1/1) is added. Stirring is continued while maintaining the liquid temperature at 95 ° C ± 2 ° C, and titration is carried out with a KMnO ₄ aqueous solution having a known concentration. At this time, the liquid color temporarily becomes violet by dropping KMnO ₄ , but slowly KMnO ₄ is added dropwise so that the violet does not continue for 30 seconds or more. In addition, since the amount of liquid is reduced by evaporation of water, pure water of 95 캜 is added so that the liquid amount is constant. The end point is where the light color is dimmed by KMnO ₄ and the pink color lasts for about 30 seconds.

In this way, the amount of KMnO ₄ consumed in the oxidation of the sample is obtained. Calculating the (n ₀ -n) from the value, and obtains a reduction rate on the basis of this.

In addition to the above-described measuring method, the reduction ratio of the shearing-sintering body before the completion of the main sintering and the sintering body after the completion of the main sintering can also be measured by the following formula.

Heated to a temperature higher than the sintering temperature at which the shear fired body or the sintered body is sintered under the condition that the constituent elements of the sample are not volatilized or dispersed, and is subjected to complete oxidation with oxygen to obtain an increased mass (amount of bonded oxygen) obtained from the value of (n ₀ -n), and based thereon calculate the reduction rate.

Since the firing atmosphere is fired in an inert gas or a preferable oxidation / reduction atmosphere, it is preferable to use a firing apparatus having a suitable seal structure and capable of sufficiently blocking contact with outside air.

The shear firing is preferably carried out under an inert gas flow so that the shear firing temperature is preferably 200 ° C. to 400 ° C. in the viewpoint of easily adjusting the obtained catalyst to a preferable redox state, Deg.] C, more preferably 300 [deg.] C to 400 [deg.] C. The pre-firing temperature is preferably maintained at a constant temperature within the range of 200 ° C to 400 ° C, but the temperature may fluctuate within the range of 200 ° C to 400 ° C, or the temperature may be gently increased or decreased. The holding time of the heating temperature is preferably 30 minutes or more, and more preferably 3 to 12 hours from the viewpoints of easily adjusting the obtained catalyst to a preferable redox state and improving the catalyst performance. The temperature pattern until reaching the shear firing temperature may be a linear heating pattern or may be a heating pattern drawing a convex arc upward or downward. Further, there may be a time to lower the temperature during the temperature rise, or the temperature rise and the temperature decrease may be repeated. Further, an endothermic reaction may occur due to the components contained in the dried powder and / or the catalyst precursor during the temperature raising process, and the temperature may be temporarily lowered.

There is no particular limitation on the average rate of temperature rise at the time of temperature rise until the shear firing temperature is reached. However, from the viewpoints of easy adjustment of the obtained catalyst to a preferable redox state and improvement of catalyst performance, 15 deg. C / min, preferably 0.5 to 5 deg. C / min, and more preferably 1 to 2 deg. C / min.

From the viewpoints of easily adjusting the obtained catalyst to a desired specific surface area, sufficiently forming an active crystal structure in the reaction, improving catalyst performance, etc., the calcination is preferably carried out under an inert gas flow, Preferably 600 to 750 占 폚, and more preferably 650 to 720 占 폚. The firing temperature is preferably maintained at a constant temperature within the range of 650 to 720 占 폚. However, the firing temperature may be varied within the range of 650 to 720 占 폚, or the temperature may be gradually increased or decreased. In addition, a period of time during which the temperature is lowered during the temperature increase may be entered, or the temperature rise and the temperature decrease may be repeated. An endothermic reaction may occur due to the components contained in the dried powder during the heating process, and the pattern of lowering the temperature may be determined depending on the situation.

The specific surface area of the catalyst can be adjusted by the firing temperature. In order to obtain a catalyst having a specific specific surface area, although it is possible to increase or decrease the specific surface area by the temperature of the shear firing, adjusting the firing temperature of the firing, which is more likely to affect the specific surface area, Is obtained.

The firing time is preferably 0.1 to 20 hours, more preferably 0.5 to 5 hours. From the viewpoint of securing at least two pieces of the shear fired body and / or the fired body in the firing tube, and securing the residence time in an appropriate firing tube such as a dry powder or the like, it is preferably 2 to 20, Passes through the zones 4 to 15 successively. The temperature can be controlled by using one or more controllers, but in order to obtain the desired firing pattern, it is preferable to provide a heater and a controller for each zone partitioned by these dicing plates. For example, in the case where seven pieces of trenches are provided so as to divide the length of a portion of the trench into the heating furnace into eight equal parts and a sintered tube divided into eight sections is used, the temperature of the partially sintered powder and / It is preferable that the set temperature is controlled by a heater and a controller provided for eight zones in each zone. For example, in the case where seven pieces are provided so as to divide the dicing plate into eight equal parts that enter the heating furnace of the firing machine and a firing unit divided into eight zones is used, the following firing pattern can be adjusted to obtain the desired firing pattern. In the case of shear firing, the temperature of the thermocouple inserted into the central portion of the shear fired body staying in the firing unit is counted from the feed side of the shear fired body, and the temperature of the thermocouple is 1: 120-280 ° C, Zone 2: 180-330 ° C, Zone 3: 250-350 占 폚 Zone 4: 270-380 占 폚 Zone 5: 300-380 占 폚 Zone 6: 300-390 占 폚 Zone 7: 320-390 占 폚 Zone 8: 260-380 占 폚 . In this firing, similarly, Zone 1: 360-560 ° C, Zone 2: 450-650 ° C, Zone 3: 600-700 ° C, Zone 4: 650-750 ° C, Zone 5: 600-700 ° C, Zone 6: 690 캜, Zone 7: 480 - 630 캜, Zone 8: 400 - 580 캜.

 The specific surface area of the shear fired body is not limited to the original firing, but can be adjusted to some extent according to the conditions of the shear firing. Although the reason for the clearness is not clear, since the reduction ratio and the specific surface area are in a proportional relationship, the range of the specific surface area can be easily made more suitable by performing the same management as described above. However, the adjustment of the specific surface area of the catalyst largely depends on the calcination method of the calcination.

Further, since the firing temperature of 650 占 폚 greatly exceeds the melting point of the oxides of the constituent metals, a large number of oxides are adhered to the wall surface of the fired tube, so that the number of blows to the main fired tube using a hammer or the like is increased, It is preferable to extend the residence time of the shear fired body. These rates of increase can be arbitrarily set from the mass balance of the amount of the shear-fired powder fed to the main firing tube and the amount of the catalyst discharged from the main firing tube. On the other hand, an oxidizing component (for example, oxygen) or a reducing component (for example, ammonia) may be added to the firing atmosphere under the inert gas flow.

The temperature rise pattern up to the main firing temperature may be raised linearly, or it may be raised by drawing a convex arc upward or downward. In addition, a period of time during which the temperature is lowered during the temperature increase may be entered, or the temperature rise and the temperature decrease may be repeated. An endothermic reaction may occur due to a component remaining in the shear fired body during the heating process, and the pattern of lowering temperature may be entered according to the situation.

The average rate of temperature rise at the time of heating up to the main baking temperature is not particularly limited, but is preferably 0.5 to 8 占 폚 / min. From the viewpoints of controlling the specific surface area, easily forming a crystal structure which is active in the reaction, improving the catalytic performance, etc., the average rate of temperature decrease after the main firing is preferably 0.05 to 50 ° C / min , More preferably 0.05 to 20 占 폚 / min. From the viewpoint of easily forming a crystal structure which is active in the reaction and improving the catalytic performance, it is also preferable to anneal while holding at a temperature lower than the sintering temperature. The holding temperature is 5 deg. C, preferably 10 deg. C, more preferably 50 deg. C lower than the main baking temperature. The holding time is preferably 0.5 hours or more, more preferably 1 hour or more, still more preferably 3 hours or more, particularly preferably 10 hours or more, from the above viewpoint.

When the firing is once again performed after the completion of the shearing firing, the firing may be performed at low temperature. The time required for the low-temperature treatment, that is, the time from the lowering of the temperature of the shear fired body and / or the fired body until the temperature is raised to the firing temperature, depends on the size, thickness, material, catalyst production amount, It is possible to appropriately adjust it in accordance with a series of periods of baking the fired body and / or the fired body, the fixing rate, the fixing amount, and the like. From the viewpoints of sufficiently peeling off the shear fatigue and / or fired body fixed to the wall surface of the fired tube, keeping the oxide layer temperature stably, and improving the performance of the obtained catalyst, the fired body is continuously fired Preferably within 30 days, more preferably within 15 days, more preferably within 3 days, particularly preferably within 2 days, in a series of periods. On the other hand, the oxide layer temperature refers to the temperature measured by the thermocouples inserted into the pre-fired powder and / or the pre-fired powder deposited in the firing unit. Further, for example, a shear-fired powder was fed at a rate of 35 kg / hr while rotating at 6 rpm by a rotary furnace having a sintered tube made of SUS having an inner diameter of 500 mm, a length of 4500 mm and a thickness of 20 mm, Deg. C, the temperature can be lowered to 400 deg. C, and then the temperature can be raised to 645 deg. C for about one day. In the case of firing continuously for one year, this low temperature treatment is carried out once a month at a frequency, whereby firing can be stably performed while maintaining the oxide layer temperature.

When an impact is applied to the firing step in the firing step, there is a tendency that the effect of causing cracks in the adhered lumps tends to be enhanced. Even in the case of performing the low temperature treatment, if a bump is applied to the firing period, It is preferable because it tends to peel off.

A projecting body is formed on the surface of the sintered body after the sintering process. Since the sintered body of the present embodiment has an adequate composition as compared with the conventional sintered body, the amount of the pores is small and the influence of the pore body is smaller than that of the conventional catalyst. However, when the sintered body exists in the reactor during the gas- It is preferable to remove it before the reaction because the side reaction is likely to occur and / or the protruding body is peeled off and the fluidity deteriorates.

By removing the pore body, it is preferable that the amount of the pore body is preferably 2 mass% or less with respect to the total mass of the sintered body. As a method of removing the pores, several methods are conceivable. Among them, a method of removing the pores by contact with the catalysts under gas flow is preferable. For example, a method of circulating a gas through a hopper or the like for storing a sintered body, or a method of putting a sintered body in a fluidized bed reactor and flowing a gas through the sintered body. The method using a fluidized bed reactor is a preferred embodiment in that a special apparatus for removing the pneumatic body is not necessary. However, since it is not a device designed by originally intended to contact the catalysts, There is a case that the pawl body can not be sufficiently removed depending on the conditions such as the amount of the catalyst, the time for circulation, the amount of the gas, and the like unless measures are taken. According to the study by the present inventors, it is possible to efficiently remove the pawl body by bringing the airflow of a sufficient flow velocity into contact with the sintered body having the pawl body. It is possible to efficiently remove the pawl body even at a large scale by providing a device having a structure capable of bringing a proper flow rate into contact with the sintered body.

For example, it has a main body for accommodating a sintered body, a sintering body returning means provided on the upper portion of the main body, and a returning means for returning the sintered body connected to the returning means, A part of the fired body in contact with the airflow in the main body is collected by the collection means, and the device returned to the main body by the return means can efficiently remove the pile body even at a large scale.

When gas is passed through a device such as a fluidized bed reactor packed with a sintered body, the sintered bodies come into contact with each other, and the projecting protrusions are removed. Since the pores formed from the sintered body are much smaller than the sintered body, they flow out of the fluidized bed reactor together with the flowing gas. It is preferable that the sintered body is filled in the apparatus so that the density of the sintered body is 300 to 1300 kg / m < 3 >. The cross-sectional area of the body portion of the apparatus to be used is preferably 0.1 to 100 m 2, more preferably 0.2 to 85 m 2.

The gas to be flowed is preferably an inert gas such as nitrogen or air. The linear velocity of the gas flowing through the body portion of the device filled with the sintered body such as the hopper or fluidized bed reactor is preferably 0.03 m / s to 5 m / s, more preferably 0.05 to 1 m / s . The flow time of the gas is preferably 1 to 168 hours. Specifically, the pawl removing apparatus of the present embodiment is provided with a main body, and the poultice is brought into contact with the fired body accommodated in the main body or the particles flowing by the air flow are brought into contact with each other, Wherein the air flow length in the direction in which the airflow flows is 10 mm or more and the average flow rate of the airflow is 15 m / / s < / RTI >

In the case of removing the pillar body in a gram scale, a sintered body is inserted into a vertical tube provided with a perforated plate having at least one hole at the bottom, a paper filter disposed at the top, and air is circulated from the bottom, It is possible to use an apparatus in which the firing bodies are brought into contact with each other by the flow of the airflow through the holes of the firing bodies and the removal of the pillar bodies.

[Warming contact ammoxidation reaction]

The gas phase contact ammoxidation reaction of the present embodiment is a process for producing an unsaturated nitrile using the above silica-supported catalyst in a process for producing a corresponding unsaturated nitrile by gas phase catalytic ammoxidation reaction of propane or isobutane.

Feedstocks for propane, isobutane, and ammonia need not necessarily be high purity, and industrial grade gases may be used. As the supplied oxygen source, air, pure oxygen or air enriched with pure oxygen can be used. Further, helium, neon, argon, carbon dioxide gas, water vapor, nitrogen and the like may be supplied as the diluting gas.

The gas phase catalytic ammoxidation reaction of propane or isobutane can be carried out under the following conditions.

The molar ratio of oxygen fed to the reaction to propane or isobutane is 0.1 to 6, preferably 0.5 to 4. The molar ratio of ammonia fed to the reaction to propane or isobutane is 0.3 to 1.5, preferably 0.7 to 1.2. The reaction temperature is 350 to 500 캜, preferably 380 to 470 캜. The reaction pressure is 5 × 10 ^{4 to} 5 × 10 ⁵ Pa, preferably 1 × 10 ⁵ to 3 × 10 ⁵ Pa. The contact time is 0.1 to 10 (sec · g / cc), preferably 0.5 to 5 (sec · g / cc).

In this embodiment, the contact time is defined by the following equation.

Contact time (sec · g / cc) = (W / F) × 273 / (273 + T)

Here, W, F and T are defined as follows.

W = amount of charged catalyst (g)

F = raw material mixed gas flow rate at standard conditions ^{(0 ℃, 1.013 × 10 5} Pa) (Ncc / sec)

T = reaction temperature (캜)

The reaction system in the gas-phase contact ammoxidation reaction may employ a conventional method such as a fixed bed, a fluid bed, and a moving bed, but a fluid bed reactor in which the reaction heat can be easily removed is preferable. The gas phase contact ammoxidation reaction may be a recycle type or a single-stream type.

Example

Hereinafter, the present embodiment will be described in more detail by way of Examples and Comparative Examples, but the scope of the present embodiment is not limited to these Examples.

In Examples and Comparative Examples, the conversion of propane, the yield of acrylonitrile, and the combustion rate of ammonia are as follows.

Propane conversion rate (%) = (moles of propane reacted) / (moles of propane supplied) x 100

Yield (%) of acrylonitrile (AN) = (number of moles of acrylonitrile produced) / (number of moles of propane supplied) x 100

Ammonia burning rate (%) = (number of moles of generated nitrogen) x 2 / (number of mols of supplied ammonia) x 100

Here, the number of moles of produced acrylonitrile and nitrogen was measured by gas chromatography.

(Example 1)

(Preparation of niobium raw material liquid)

A niobium raw material liquid was prepared in the following manner. To 500 kg of water, 76.33 kg of niobic acid containing 80.2% by mass of Nb ₂ O ₅ and 290.2 kg of oxalic acid dihydrate [H ₂ C ₂ O ₄ .2H ₂ O] were mixed. The molar ratio of oxalic acid / niobium added was 5.0, and the concentration of niobium was 0.532 (mol-Nb / kg-solution).

This solution was heated and stirred at 95 DEG C for 1 hour to obtain an aqueous solution in which the niobium compound was dissolved. After the aqueous solution was allowed to cool and ice-cooled, the solid was filtered off by suction filtration to obtain a uniform niobium compound aqueous solution. The same operation was repeated several times, and the resulting niobium compound aqueous solution was combined into one raw niobium solution. The molar ratio of oxalic acid / niobium of this niobium raw material liquid was 2.40 by the following analysis.

It refers forward this niobium raw material liquid 10 g of the crucible, and then dried overnight at 95 ℃, and heat treated for one hour at _{600 ℃, Nb 2 O 5 0.8323} g was obtained. From this result, the niobium concentration was 0.626 (mol-Nb / kg-solution).

3 g of the niobium raw material liquid was quenched into a 300 mL glass beaker, 200 mL of hot water at about 80 캜 was added, and then 10 mL of 1: 1 sulfuric acid was added. The obtained solution was titrated with 1/4 defined KMnO ₄ while stirring at a liquid temperature of 70 캜 on a hot stirrer. The place where the faint light pink by KMnO ₄ continued for about 30 seconds or more was made as the end point. The concentration of oxalic acid was 1.50 (mol-oxalic acid / kg) as calculated from the appropriate amount according to the following equation.

2KMnO ₄ + 3H ₂ SO ₄ + 5H ₂ C ₂ O ₄ → K ₂ SO ₄ + 2MnSO ₄ + 10CO ₂ + 8H ₂ O

The obtained niobium raw material liquid was used as a niobium raw material liquid in the production of the following oxide catalyst.

(Combination of the raw material combination liquid in the combination tank)

To 100 kg of water were added 19.9 kg of ammonium heptamolybdate [(NH ₄ ) ₆ Mo ₇ O ₂₄ .4H ₂ O], 2.75 kg of ammonium metavanadate [NH ₄ VO ₃ ], 2,000 g of antimony trioxide [Sb ₂ O ₃ ] , 3.25 kg of cerium nitrate [Ce (NO ₃ ) ₃ .6H ₂ O] and 495 g of cerium nitrate [Ce (NO ₃ ) ₃ .6H ₂ O] were dissolved in 2 kg of water and heated at 95 ° C for 1 hour with stirring to obtain a raw material combination solution .

To 15.9 kg of the niobium raw material liquid, 2.28 kg of hydrogen peroxide aqueous solution containing 30 mass% as H ₂ O ₂ was added. The liquid temperature was maintained at approximately 20 占 폚 and stirred and mixed to obtain a raw material combination solution (II).

The obtained raw material combination solution (I) After cooling to 70 ℃, SiO ₂ average primary particle diameter of the sol having an average primary particle diameter of 50 nm containing a 30.2 wt% silica 34.2 kg and containing 30.0% by mass as SiO ₂ as a 3.60 kg of 18 nm silica sol was added. Then, 3.80 kg of hydrogen peroxide aqueous solution containing 30% by mass of H ₂ O ₂ was added and stirred at 55 ° C for 30 minutes. Then 516 g (50% purity) of the raw material combination solution (II) and the aqueous ammonium metatungstate solution were added, ). Further, 8.60 kg of powdered silica was dispersed in 77.4 kg of water and aged at 50 캜 for 1 hour as it was to obtain a raw material combination solution (III).

(Spray drying of the raw material combination liquid obtained in the combination tank)

Before the completion of the combination of the raw material combination liquid (III), hot air of 50 ° C adjusted to a feed rate of 80 kg / Hr and air heated to 210 ° C was supplied to the centrifugal spray dryer, Lt; / RTI >

The supply amount of the raw material combination liquid to be supplied to the spray dryer was adjusted so that the outlet temperature of the spray dryer was not changed, and the supply amount was 100 kg / Hr. In the meantime, the outlet temperature was 120 ± 5 ° C and there was no significant variation.

(Measurement of ultraviolet visible spectrum)

The obtained dried product was sampled every day, and 0.5 g of the obtained 10 sample products was measured by a diffuse reflection method in a range of 200 to 800 nm using JASCO UV / VIS Spectrometer V-650 manufactured by Nihon Bunko Co., Ltd. Spectralon manufactured by Labspere was used as a standard material for the baseline. The maximum absorbance was 1.02. The absorbance at 600 nm was 0.31 to 0.36, which was the absorbance with which high performance could be expected with reference to the description of JP-A-2009-148749. Therefore, the obtained spray dried product was used for classification operation without sorting.

(Classification operation)

The dried product thus obtained was classified using a sieve having a sieve size of 25 mu m to obtain a powder. The content of the particles of 25 mu m or less in the obtained powder was 0.8 mass% and the average particle diameter was 55 mu m.

(Firing of powder)

Seven slabs each having a height of 150 mm in a cylindrical sintered tube made of SUS having an inner diameter of 500 mm, a length of 3500 mm and a thickness of 20 mm were set so as to divide the length of the heating furnace into eight equal parts at a rate of 20 kg / hr And heated to 370 캜 for about 4 hours while rotating the fired tube at 4 rpm under a nitrogen gas flow of 600 N 터 l / min and heated to a heating furnace temperature of 370 캜 for 3 hours, And a shear fired product was obtained by shearing firing. Seven slabs each having a height of 150 mm in an SUS-made sintered pipe having an inner diameter of 500 mm, a length of 3500 mm and a thickness of 20 mm were installed so as to divide the length of the heating furnace into 8 equal parts. The sintering tube was rotated at 4 rpm , And shear debris was distributed at a rate of 15 kg / hr. At that time, with a hammering device provided with a hammer having a mass of 14 kg, which is made of stainless steel and the tip of the striking part was provided, the portion of the sintered tube on the powder introduction side (the portion not covered with the heating furnace) A temperature profile at which the temperature was raised to 690 캜 at a rate of 2 캜 / min under a nitrogen gas flow of 500 N / min while being blown once at a rate of 5 캜 for 5 seconds and then fired at 690 캜 for 2 hours, The temperature of the furnace was adjusted so that the oxide catalyst was obtained.

(Composition of oxide catalyst)

As a result of analyzing the composition of the oxide catalyst, the composition of the metal oxide was MoV _0.21 Nb _0.09 Sb _0.20 W _0.01 Ce _0.01 . The amount of silica supported was 47 mass% with respect to the total mass of the catalyst composed of the metal oxide and silica.

(Measurement of specific surface area)

The specific surface area was measured by BET 1-point method using Gemini 2360 manufactured by MICROMETRICS.

The specific surface area was 10.8 m < 2 > / g.

(Removal of the stone body)

50 g of an oxide catalyst was injected into a vertical tube (inner diameter 41.6 mm, length 70 cm) equipped with a perforated disk having three holes with a diameter of 1/64 inch on the bottom and a paper filter on the top. At this time, the airflow length in the flow direction of the airflow was 52 mm and the average linear velocity of the airflow was 310 m / s. When the oxide catalyst obtained after 24 hours was confirmed by SEM, the protrusions did not exist on the surface of the oxide catalyst.

(Total pore volume)

The total pore volume was determined by mercury porosimeter.

The total pore volume was 0.297 cm 3 / g.

(Pore distribution)

Pore distribution was determined by mercury porosimeter.

The ratio of the pore volume of pores having a pore diameter of less than 60 nm was 3.9%, and the ratio of pore volume of pores having a pore diameter of 120 nm or more was 1.0%.

(Calculation of average pore diameter)

The average pore diameter was calculated using equation (i), assuming that the pores are cylindrical.

D = 4V / S (i)

Here, D: average pore diameter (m), V: total pore volume (m 3 / g), and S: specific surface area (m 2 / g).

The calculated average pore diameter was 110 nm.

(Measurement of crystallite size)

The measurement conditions of the X-ray are as follows: Apparatus: RIGAKU RINT2500HF / PC, Light source: Kα line of Cu, Output: 40 kV-20 mA, Measurement range (2θ): 5 to 50 °, Scan speed: 1 deg / min , And the number of integration: 4 times. In order to obtain the exact half-value width, before the measurement of the sample, the standard reference material (LaB6) was used to correct the enlargement of the half-value width inherent to the apparatus.

The crystallite size was calculated by Scherr's equation (ii) from the half-value width of the (001) peak (plane interval d = 4.02) obtained by X-ray diffraction.

L = 0.9? /? Cos? (Ii)

Here, L is the crystallite size (Å), λ is the wavelength (Å), β is the diffraction line width (rad), and θ is the diffraction angle (rad).

The calculated crystallite size was 106 nm.

(Ammoxidation reaction of propane)

Using the oxide catalyst obtained above, propane was provided to the vapor-phase ammoxidation reaction by the following method. A mixed gas of propane: ammonia: oxygen: helium = 1: 1: 3: 18 in a molar ratio of propane: ammonia: oxygen: helium = 1 was prepared under a reaction pressure of 440 ° C at a reaction temperature of 440 ° C. Contact time 2.8 (sec · g / cc). After the reaction, the conversion of propane was 89.8%, the yield of acrylonitrile was 54.8%, and the combustion rate of ammonia was 18.8%.

(Example 2)

(Crude solution of niobium raw material liquid)

The liquid was adjusted in the same manner as in Example 1.

(Combination of raw material combination liquid in the combination tank)

To 100 kg of water were added 19.9 kg of ammonium heptamolybdate [(NH ₄ ) ₆ Mo ₇ O ₂₄ .4H ₂ O], 2.75 kg of ammonium metavanadate [NH ₄ VO ₃ ], 2,000 g of antimony trioxide [Sb ₂ O ₃ ] , 3.25 kg of cerium nitrate [Ce (NO ₃ ) ₃ .6H ₂ O] and 495 g of cerium nitrate [Ce (NO ₃ ) ₃ .6H ₂ O] were dissolved in 2 kg of water and heated at 95 ° C for 1 hour with stirring to obtain a raw material combination solution .

To 15.95 kg of the raw niobium solution was added 2.28 kg of hydrogen peroxide solution containing 30 mass% as H ₂ O ₂ . The liquid temperature was maintained at approximately 20 占 폚 and stirred and mixed to obtain a raw material combination solution (II).

Obtained after cooling the material combination solution (I) to 70 ℃, SiO ₂ average primary particle diameter with a sol having an average primary particle diameter of 23 nm containing a 30.2 wt% silica 31.0 kg, containing 30.0% by mass as SiO ₂ as a 6.80 kg of 13 nm silica sol was added. Then, 3.80 kg of hydrogen peroxide aqueous solution containing 30% by mass of H ₂ O ₂ was added and stirred at 55 ° C for 30 minutes. Then 516 g (50% purity) of the raw material combination solution (II) and the aqueous ammonium metatungstate solution were added, ). Further, 8.60 kg of powdered silica was dispersed in 77.4 kg of water and aged at 50 캜 for 1 hour as it was to obtain a raw material combination solution (III).

(Spray drying of the raw material combination liquid obtained in the combination tank)

Before the completion of the combination of the raw material combination liquid (III), hot air of 50 ° C adjusted to a feed rate of 80 kg / Hr and air heated to 210 ° C was supplied to the centrifugal spray dryer, Lt; / RTI >

The supply amount of the raw material combination liquid to be supplied to the spray dryer was adjusted so that the outlet temperature of the spray dryer was not changed, and the supply amount was 100 kg / Hr. In the meantime, the outlet temperature was 120 ± 5 ° C and there was no significant variation.

(Measurement of ultraviolet visible spectrum)

The obtained dried product was sampled every day, and 0.5 g of the obtained 10 sample products was measured by a diffuse reflection method in a range of 200 to 800 nm using JASCO UV / VIS Spectrometer V-650 manufactured by Nihon Bunko Co., Ltd. Spectralon manufactured by Labspere was used as a standard material for the baseline. The maximum absorbance was 1.02. The absorbance at 600 nm was 0.31 to 0.36, which was the absorbance with which high performance could be expected with reference to the description of JP-A-2009-148749. Therefore, the obtained spray dried product was used for classification operation without sorting.

(Classification operation)

The dried product thus obtained was classified using a sieve having a sieve size of 25 mu m to obtain a powder. The content of the particles of 25 mu m or less in the obtained powder was 0.8 mass% and the average particle diameter was 55 mu m.

(Firing of powder)

Seven slabs each having a height of 150 mm in a cylindrical sintered tube made of SUS having an inner diameter of 500 mm, a length of 3500 mm and a thickness of 20 mm were set so as to divide the length of the heating furnace into eight equal parts at a rate of 20 kg / hr And heated to 370 캜 for about 4 hours while rotating the fired tube at 4 rpm under a nitrogen gas flow of 600 N 터 l / min and heated to a heating furnace temperature of 370 캜 for 3 hours, And a shear fired product was obtained by shearing firing. Seven slabs each having a height of 150 mm in an SUS-made sintered pipe having an inner diameter of 500 mm, a length of 3500 mm and a thickness of 20 mm were installed so as to divide the length of the heating furnace into 8 equal parts. The sintering tube was rotated at 4 rpm , And shear debris was distributed at a rate of 15 kg / hr. At that time, with a hammering device provided with a hammer having a mass of 14 kg, which is a SUS-made tip end of the striking part, on the powder introduction side of the firing tube (the part not covered with the heating furnace) A temperature profile at which the temperature was raised to 685 캜 at a rate of 2 캜 / min under a nitrogen gas flow of 500 N / min while being blown once at a rate of 5 캜 for 5 seconds, followed by baking at 685 캜 for 2 hours, The temperature of the furnace was adjusted so that the oxide catalyst was obtained.

(Composition of oxide catalyst)

As a result of analyzing the composition of the oxide catalyst, the composition of the metal oxide was MoV _0.21 Nb _0.09 Sb _0.20 W _0.01 Ce _0.01 . The amount of silica supported was 47 mass% with respect to the total mass of the catalyst composed of the metal oxide and silica.

(Measurement of specific surface area)

As a result of measurement by the same method as in Example 1, the specific surface area was 12.8 m 2 / g.

(Removal of the stone body)

Was removed in the same manner as in Example 1.

(Total pore volume)

As a result of measurement by the same method as in Example 1, the total pore volume was 0.288 cm 3 / g.

(Pore distribution)

The ratio of the pore volume of the pores having a pore diameter of less than 60 nm was 6.8%, and the ratio of the pore volume of the pores having a pore diameter of 120 nm or more was 0.6%.

(Calculation of average pore diameter)

As a result of measurement by the same method as in Example 1, the average pore diameter was 90 nm.

(Measurement of crystallite size)

As a result of measurement by the same method as in Example 1, the crystallite size was 98 nm.

(Ammoxidation reaction of propane)

Using the oxide catalyst obtained above, propane was provided for the vapor-phase ammoxidation reaction by the following method. A mixed gas of propane: ammonia: oxygen: helium = 1: 1: 3: 18 in a molar ratio of propane: ammonia: oxygen: helium = 1 was prepared under a reaction pressure of 440 ° C at a reaction temperature of 440 ° C. Contact time 2.8 (sec · g / cc). After the reaction, the conversion of propane was 90.1%, the yield of acrylonitrile was 54.9%, and the combustion rate of ammonia was 18.6%.

(Example 3)

(Crude solution of niobium raw material liquid)

The liquid was adjusted in the same manner as in Example 1.

(Combination of raw material combination liquid in the combination tank)

To 100 kg of water were added 19.9 kg of ammonium heptamolybdate [(NH ₄ ) ₆ Mo ₇ O ₂₄ .4H ₂ O], 2.75 kg of ammonium metavanadate [NH ₄ VO ₃ ], 2,000 g of antimony trioxide [Sb ₂ O ₃ ] , 3.25 kg of cerium nitrate [Ce (NO ₃ ) ₃ .6H ₂ O] and 495 g of cerium nitrate [Ce (NO ₃ ) ₃ .6H ₂ O] were dissolved in 2 kg of water and heated at 95 ° C for 1 hour with stirring to obtain a raw material combination solution .

To 15.95 kg of the raw niobium solution was added 2.28 kg of hydrogen peroxide solution containing 30 mass% as H ₂ O ₂ . The liquid temperature was maintained at approximately 20 占 폚 and stirred and mixed to obtain a raw material combination solution (II).

The obtained raw material combination solution (I) After cooling to 70 ℃, SiO ₂ average primary particle diameter of the sol having an average primary particle diameter of 25 nm containing a 30.2 wt% silica 25.3 kg and containing 30.0% by mass as SiO ₂ as a 12.5 kg of 10 nm silica sol was added. Then, 3.80 kg of hydrogen peroxide aqueous solution containing 30% by mass of H ₂ O ₂ was added and stirred at 55 ° C for 30 minutes. Then 516 g (50% purity) of the raw material combination solution (II) and the aqueous ammonium metatungstate solution were added, ). Further, 8.60 kg of powdered silica was dispersed in 77.4 kg of water and aged at 50 캜 for 1 hour as it was to obtain a raw material combination solution (III).

(Spray drying of the raw material combination liquid obtained in the combination tank)

Before the completion of the combination of the raw material combination liquid (III), hot air of 50 ° C adjusted to a feed rate of 80 kg / Hr and air heated to 210 ° C was supplied to the centrifugal spray dryer, Lt; / RTI >

The supply amount of the raw material combination liquid to be supplied to the spray dryer was adjusted so that the outlet temperature of the spray dryer was not changed, and the supply amount was 100 kg / Hr. In the meantime, the outlet temperature was 120 ± 5 ° C and there was no significant variation.

(Measurement of ultraviolet visible spectrum)

The obtained dried product was sampled every day, and 0.5 g of the obtained 10 sample products was measured by a diffuse reflection method in a range of 200 to 800 nm using JASCO UV / VIS Spectrometer V-650 manufactured by Nihon Bunko Co., Ltd. Spectralon manufactured by Labspere was used as a standard material for the baseline. The maximum absorbance was 1.02. The absorbance at 600 nm was 0.31 to 0.36, which was the absorbance with which high performance could be expected with reference to the description of JP-A-2009-148749. Therefore, the obtained spray dried product was used for classification operation without sorting.

(Classification operation)

The dried product thus obtained was classified using a sieve having a sieve size of 25 mu m to obtain a powder. The content of the particles of 25 mu m or less in the obtained powder was 0.8 mass% and the average particle diameter was 55 mu m.

(Firing of powder)

And fired in the same manner as in Example 2. [

(Composition of oxide catalyst)

As a result of analyzing the composition of the oxide catalyst, the composition of the metal oxide was MoV _0.21 Nb _0.09 Sb _0.20 W _0.01 Ce _0.01 . The amount of silica supported was 47 mass% with respect to the total mass of the catalyst composed of the metal oxide and silica.

(Measurement of specific surface area)

As a result of measurement by the same method as in Example 1, the specific surface area was 13.6 m < 2 > / g.

(Removal of the stone body)

Was removed in the same manner as in Example 1.

(Total pore volume)

As a result of measurement by the same method as in Example 1, the total pore volume was 0.221 cm 3 / g.

(Pore distribution)

The ratio of the pore volume of the pores having a pore diameter of less than 60 nm was 18.7%, and the ratio of the pore volume of the pores having a pore diameter of 120 nm or more was 0.2%.

(Calculation of average pore diameter)

As a result of measurement by the same method as in Example 1, the average pore diameter was 65 nm.

(Measurement of crystallite size)

As a result of measurement by the same method as in Example 1, the crystallite size was 102 nm.

(Ammoxidation reaction of propane)

Using the oxide catalyst obtained above, propane was provided for the vapor-phase ammoxidation reaction by the following method. A mixed gas of propane: ammonia: oxygen: helium = 1: 1: 3: 18 in a molar ratio of propane: ammonia: oxygen: helium = 1 was prepared under a reaction pressure of 440 ° C at a reaction temperature of 440 ° C. Contact time 2.8 (sec · g / cc). After the reaction, the conversion of propane was 88.5% and the yield of acrylonitrile was 54.7%. The reaction was carried out for 3 months, and the yield of acrylonitrile was 54.7% and the combustion rate of ammonia was 19.4%.

(Example 4)

(Crude solution of niobium raw material liquid)

The liquid was adjusted in the same manner as in Example 1.

(Combination of raw material combination liquid in the combination tank)

To 100 kg of water, 19.9 kg of ammonium heptamolybdate [(NH ₄ ) ₆ Mo ₇ O ₂₄ .4H ₂ O], 2.75 kg of ammonium metavanadate [NH ₄ VO ₃ ], and tellurium trioxide [TeO ₃ ] 1.96 kg of cerium nitrate [Ce (NO ₃ ) ₃ .6H ₂ O], and 495 g of cerium nitrate [Ce (NO ₃ ) ₃ .6H ₂ O] were dissolved in 2 kg of water and heated at 95 ° C for 1 hour while stirring to obtain a raw material combination solution .

To 15.95 kg of the raw niobium solution was added 2.28 kg of hydrogen peroxide solution containing 30 mass% as H ₂ O ₂ . The liquid temperature was maintained at approximately 20 占 폚 and stirred and mixed to obtain a raw material combination solution (II).

The obtained raw material combination solution (I) After cooling to 70 ℃, SiO ₂ average primary particle diameter with a sol having an average primary particle diameter of 45 nm containing a 30.2 wt% silica 31.0 kg, containing 30.0% by mass as SiO ₂ as a 7.70 kg of 15 nm silica sol were added. Then, 3.80 kg of hydrogen peroxide aqueous solution containing 30% by mass of H ₂ O ₂ was added and stirred at 55 ° C for 30 minutes. Then 516 g (50% purity) of the raw material combination solution (II) and the aqueous ammonium metatungstate solution were added, ). Further, 8.60 kg of powdered silica was dispersed in 77.4 kg of water and aged at 50 캜 for 1 hour as it was to obtain a raw material combination solution (III).

(Spray drying of the raw material combination liquid obtained in the combination tank)

Before the completion of the combination of the raw material combination liquid (III), hot air of 50 ° C adjusted to a feed rate of 80 kg / Hr and air heated to 210 ° C was supplied to the centrifugal spray dryer, Lt; / RTI >

The supply amount of the raw material combination liquid to be supplied to the spray dryer was adjusted so that the outlet temperature of the spray dryer was not changed, and the supply amount was 100 kg / Hr. In the meantime, the outlet temperature was 120 ± 5 ° C and there was no significant variation.

(Measurement of ultraviolet visible spectrum)

The obtained dried product was sampled every day, and 0.5 g of the obtained 10 sample products was measured by a diffuse reflection method in a range of 200 to 800 nm using JASCO UV / VIS Spectrometer V-650 manufactured by Nihon Bunko Co., Ltd. Spectralon manufactured by Labspere was used as a standard material for the baseline. The maximum absorbance was 1.02. The absorbance at 600 nm was 0.31 to 0.36, which was the absorbance with which high performance could be expected with reference to the description of JP-A-2009-148749. Therefore, the obtained spray dried product was used for classification operation without sorting.

(Classification operation)

The dried product thus obtained was classified using a sieve having a sieve size of 25 mu m to obtain a powder. The content of the particles of 25 mu m or less in the obtained powder was 0.8 mass% and the average particle diameter was 55 mu m.

(Firing of powder)

Seven slabs each having a height of 150 mm in a cylindrical sintered tube made of SUS having an inner diameter of 500 mm, a length of 3500 mm and a thickness of 20 mm were set so as to divide the length of the heating furnace into eight equal parts at a rate of 20 kg / hr And heated to 370 캜 for about 4 hours while rotating the fired tube at 4 rpm under a nitrogen gas flow of 600 N 터 l / min and heated to a heating furnace temperature of 370 캜 for 3 hours, And a shear fired product was obtained by shearing firing. Seven slabs each having a height of 150 mm in an SUS-made sintered pipe having an inner diameter of 500 mm, a length of 3500 mm and a thickness of 20 mm were installed so as to divide the length of the heating furnace into 8 equal parts. The sintering tube was rotated at 4 rpm , And shear debris was distributed at a rate of 15 kg / hr. At that time, with a hammering device provided with a hammer having a mass of 14 kg, which is made of stainless steel and the tip of the striking part was provided, the portion of the sintered tube on the powder introduction side (the portion not covered with the heating furnace) A temperature profile at which the temperature was raised to 690 캜 at a rate of 2 캜 / min under a nitrogen gas flow of 500 N / min while being blown once at a rate of 5 캜 from the height for 3 hours at 690 캜, The temperature of the furnace was adjusted so that the oxide catalyst was obtained.

(Composition of oxide catalyst)

As a result of analyzing the composition of the oxide catalyst, the composition of the metal oxide was MoV _0.21 Nb _0.09 Te _0.20 W _0.01 Ce _0.01 . The amount of silica supported was 47 mass% with respect to the total mass of the catalyst composed of the metal oxide and silica.

(Measurement of specific surface area)

As a result of measurement by the same method as in Example 1, the specific surface area was 10.2 m < 2 > / g.

(Removal of the stone body)

Was removed in the same manner as in Example 1.

(Total pore volume)

As a result of measurement by the same method as in Example 1, the total pore volume was 0.235 cm 3 / g.

(Pore distribution)

As a result of measurement by the same method as in Example 1, the ratio of the pore volume of pores having a pore diameter of less than 60 nm was 7.1%, and the ratio of pore volume of pores having a pore diameter of 120 nm or more was 0.7%.

(Calculation of average pore diameter)

As a result of measurement by the same method as in Example 1, the average pore diameter was 92 nm.

(Measurement of crystallite size)

As a result of measurement by the same method as in Example 1, the crystallite size was 185 nm.

(Ammoxidation reaction of propane)

Using the oxide catalyst obtained above, propane was provided for the vapor-phase ammoxidation reaction by the following method. A mixed gas of propane: ammonia: oxygen: helium = 1: 1: 3: 18 in a molar ratio of propane: ammonia: oxygen: helium = 1 was prepared under a reaction pressure of 440 ° C at a reaction temperature of 440 ° C. Contact time 2.8 (sec · g / cc). After the reaction, the conversion of propane was 88.8%, the yield of acrylonitrile was 54.8%, and the combustion rate of ammonia was 19.0%.

(Example 5)

(Crude solution of niobium raw material liquid)

The liquid was adjusted in the same manner as in Example 1.

(Combination of raw material combination liquid in the combination tank)

To 100 kg of water were added 19.9 kg of ammonium heptamolybdate [(NH ₄ ) ₆ Mo ₇ O ₂₄ .4H ₂ O], 2.75 kg of ammonium metavanadate [NH ₄ VO ₃ ], 2,000 g of antimony trioxide [Sb ₂ O ₃ ] , 3.25 kg of cerium nitrate [Ce (NO ₃ ) ₃ .6H ₂ O] and 495 g of cerium nitrate [Ce (NO ₃ ) ₃ .6H ₂ O] were dissolved in 2 kg of water and heated at 95 ° C for 1 hour with stirring to obtain a raw material combination solution .

To 15.95 kg of the raw niobium solution was added 2.28 kg of hydrogen peroxide solution containing 30 mass% as H ₂ O ₂ . The liquid temperature was maintained at approximately 20 占 폚 and stirred and mixed to obtain a raw material combination solution (II).

After cooling the obtained raw material combination solution (I) to 70 캜, 31.0 kg of silica sol containing 30.2% by mass of SiO ₂ and having an average primary particle diameter of 50 nm and 30.0% by mass of SiO ₂ and having an average primary particle diameter 6.80 kg of 18 nm silica sol was added. Subsequently, 3.80 kg of hydrogen peroxide aqueous solution containing 30% by mass of H ₂ O ₂ was added and stirred and mixed at 55 ° C for 30 minutes. Then, 258 g (50% purity) of the raw material combination solution (II) and the aqueous ammonium metatungstate solution were added, ) And titanium oxide [TiO ₂ ] (18.2 g). Further, 8.60 kg of powdered silica was dispersed in 77.4 kg of water and aged at 50 캜 for 1 hour as it was to obtain a raw material combination solution (III).

(Spray drying of the raw material combination liquid obtained in the combination tank)

Before the completion of the combination of the raw material combination liquid (III), hot air of 50 ° C adjusted to a feed rate of 80 kg / Hr and air heated to 210 ° C was supplied to the centrifugal spray dryer, Lt; / RTI >

The supply amount of the raw material combination liquid to be supplied to the spray dryer was adjusted so that the outlet temperature of the spray dryer was not changed, and the supply amount was 100 kg / Hr. In the meantime, the outlet temperature was 120 ± 5 ° C and there was no significant variation.

(Measurement of ultraviolet visible spectrum)

The obtained dried product was sampled every day, and 0.5 g of the obtained 10 sample products was measured by a diffuse reflection method in a range of 200 to 800 nm using JASCO UV / VIS Spectrometer V-650 manufactured by Nihon Bunko Co., Ltd. Spectralon manufactured by Labspere was used as a standard material for the baseline. The maximum absorbance was 1.02. The absorbance at 600 nm was 0.31 to 0.36, which was the absorbance with which high performance could be expected with reference to the description of JP-A-2009-148749. Therefore, the obtained spray dried product was used for classification operation without sorting.

(Classification operation)

The dried product thus obtained was classified using a sieve having a sieve size of 25 mu m to obtain a powder. The content of the particles of 25 mu m or less in the obtained powder was 0.8 mass% and the average particle diameter was 55 mu m.

(Firing of powder)

And fired in the same manner as in Example 2. [

(Composition of oxide catalyst)

As a result of analyzing the composition of the oxide catalyst, the composition of the metal oxide was MoV _0.21 Nb _0.09 Sb _0.20 W _0.005 Ti _0.002 Ce _0.01 . The amount of silica supported was 47 mass% with respect to the total mass of the catalyst composed of the metal oxide and silica.

(Measurement of specific surface area)

As a result of measurement by the same method as in Example 1, the specific surface area was 12.8 m 2 / g.

(Removal of the stone body)

Was removed in the same manner as in Example 1.

(Total pore volume)

As a result of measurement by the same method as in Example 1, the total pore volume was 0.288 cm 3 / g.

(Pore distribution)

The ratio of the pore volume of the pores having a pore diameter of less than 60 nm was 6.6%, and the ratio of the pore volume of the pores having a pore diameter of 120 nm or more was 0.5%.

(Calculation of average pore diameter)

As a result of measurement by the same method as in Example 1, the average pore diameter was 90 nm.

(Measurement of crystallite size)

As a result of measurement by the same method as in Example 1, the crystallite size was 98 nm.

(Ammoxidation reaction of propane)

Using the oxide catalyst obtained above, propane was provided for the vapor-phase ammoxidation reaction by the following method. A mixed gas of propane: ammonia: oxygen: helium = 1: 1: 3: 18 in a molar ratio of propane: ammonia: oxygen: helium = 1 was prepared under a reaction pressure of 440 ° C at a reaction temperature of 440 ° C. Contact time 2.8 (sec · g / cc). After the reaction, the conversion of propane was 88.8%, the yield of acrylonitrile was 54.6%, and the combustion rate of ammonia was 19.5%.

(Example 6)

(Crude solution of niobium raw material liquid)

The liquid was adjusted in the same manner as in Example 1.

(Combination of raw material combination liquid in the combination tank)

To 100 kg of water were added 19.9 kg of ammonium heptamolybdate [(NH ₄ ) ₆ Mo ₇ O ₂₄ .4H ₂ O], 2.75 kg of ammonium metavanadate [NH ₄ VO ₃ ], 2,000 g of antimony trioxide [Sb ₂ O ₃ ] , 3.25 kg of cerium nitrate [Ce (NO ₃ ) ₃ .6H ₂ O] and 495 g of cerium nitrate [Ce (NO ₃ ) ₃ .6H ₂ O] were dissolved in 2 kg of water and heated at 95 ° C for 1 hour with stirring to obtain a raw material combination solution .

To 15.95 kg of the raw niobium solution was added 2.28 kg of hydrogen peroxide solution containing 30 mass% as H ₂ O ₂ . The liquid temperature was maintained at approximately 20 占 폚 and stirred and mixed to obtain a raw material combination solution (II).

Obtained after cooling the material combination solution (I) to 70 ℃, the average primary particle diameter of 18, containing 30.0 weight% in terms of average primary particle diameter of the sol of 50 nm silica 31.0 kg and SiO ₂ containing 30.2% by mass as SiO ₂ nm < / RTI > of silica sol. Subsequently, 3.80 kg of hydrogen peroxide aqueous solution containing 30% by mass of H ₂ O ₂ was added and stirred and mixed at 55 ° C for 30 minutes. Then, 258 g (50% purity) of the raw material combination solution (II) and the aqueous ammonium metatungstate solution were added, ) And manganese oxide [MnO ₂ ] were added. Further, 8.60 kg of powdered silica was dispersed in 77.4 kg of water and aged at 50 캜 for 1 hour as it was to obtain a raw material combination solution (III).

(Spray drying of the raw material combination liquid obtained in the combination tank)

Before the completion of the combination of the raw material combination liquid (III), hot air of 50 ° C adjusted to a feed rate of 80 kg / Hr and air heated to 210 ° C was supplied to the centrifugal spray dryer, Lt; / RTI >

The supply amount of the raw material combination liquid to be supplied to the spray dryer was adjusted so that the outlet temperature of the spray dryer was not changed, and the supply amount was 100 kg / Hr. In the meantime, the outlet temperature was 120 ± 5 ° C and there was no significant variation.

(Measurement of ultraviolet visible spectrum)

The obtained dried product was sampled every day, and 0.5 g of the obtained 10 sample products was measured by a diffuse reflection method in a range of 200 to 800 nm using JASCO UV / VIS Spectrometer V-650 manufactured by Nihon Bunko Co., Ltd. Spectralon manufactured by Labspere was used as a standard material for the baseline. The maximum absorbance was 1.02. The absorbance at 600 nm was 0.31 to 0.36, which was the absorbance with which high performance could be expected with reference to the description of JP-A-2009-148749. Therefore, the obtained spray dried product was used for classification operation without sorting.

(Classification operation)

The dried product thus obtained was classified using a sieve having a sieve size of 25 mu m to obtain a powder. The content of the particles of 25 mu m or less in the obtained powder was 0.8 mass% and the average particle diameter was 55 mu m.

(Firing of powder)

And fired in the same manner as in Example 2. [

(Composition of oxide catalyst)

As a result of analyzing the composition of the oxide catalyst, the composition of the metal oxide was MoV _0.21 Nb _0.09 Sb _0.20 W _0.005 Mn _0.003 Ce _0.01 . The amount of silica supported was 47 mass% with respect to the total mass of the catalyst composed of the metal oxide and silica.

(Measurement of specific surface area)

As a result of measurement by the same method as in Example 1, the specific surface area was 13.2 m < 2 > / g.

(Removal of the stone body)

Was removed in the same manner as in Example 1.

(Total pore volume)

As a result of measurement by the same method as in Example 1, the total pore volume was 0.304 cm 3 / g.

(Pore distribution)

The ratio of the pore volume of the pores having a pore diameter of less than 60 nm was 6.9%, and the ratio of the pore volume of the pores having a pore diameter of 120 nm or more was 0.6%.

(Calculation of average pore diameter)

As a result of measurement by the same method as in Example 1, the average pore diameter was 92 nm.

(Measurement of crystallite size)

As a result of measurement by the same method as in Example 1, the crystallite size was 101 nm.

(Ammoxidation reaction of propane)

Using the oxide catalyst obtained above, propane was provided for the vapor-phase ammoxidation reaction by the following method. A mixed gas of propane: ammonia: oxygen: helium = 1: 1: 3: 18 in a molar ratio of propane: ammonia: oxygen: helium = 1 was prepared under a reaction pressure of 440 ° C at a reaction temperature of 440 ° C. Contact time 2.8 (sec · g / cc). After the reaction, the conversion of propane was 88.8%, the yield of acrylonitrile was 54.7%, and the combustion rate of ammonia was 19.3%.

(Example 7)

(Crude solution of niobium raw material liquid)

The liquid was adjusted in the same manner as in Example 1.

(Combination of raw material combination liquid in the combination tank)

To 100 kg of water were added 19.9 kg of ammonium heptamolybdate [(NH ₄ ) ₆ Mo ₇ O ₂₄ .4H ₂ O], 2.75 kg of ammonium metavanadate [NH ₄ VO ₃ ], 2,000 g of antimony trioxide [Sb ₂ O ₃ ] , 3.25 kg of cerium nitrate [Ce (NO ₃ ) ₃ .6H ₂ O] and 495 g of cerium nitrate [Ce (NO ₃ ) ₃ .6H ₂ O] were dissolved in 2 kg of water and heated at 95 ° C for 1 hour with stirring to obtain a raw material combination solution .

To 15.95 kg of the raw niobium solution was added 2.28 kg of hydrogen peroxide solution containing 30 mass% as H ₂ O ₂ . The liquid temperature was maintained at approximately 20 占 폚 and stirred and mixed to obtain a raw material combination solution (II).

After cooling the obtained raw material combination solution (I) to 70 캜, 31.0 kg of silica sol containing 30.2% by mass of SiO ₂ and having an average primary particle diameter of 50 nm and 30.0% by mass of SiO ₂ and having an average primary particle diameter 6.80 kg of 18 nm silica sol was added. Subsequently, 3.80 kg of hydrogen peroxide aqueous solution containing 30% by mass of H ₂ O ₂ was added and stirred and mixed at 55 ° C for 30 minutes. Then, 155 g (50% purity) of the raw material combination solution (II) and the aqueous ammonium metatungstate solution was added, ) And bismuth nitrate [Bi (NO ₃ ) ₃ .5H ₂ O] were added. Further, 8.60 kg of powdered silica was dispersed in 77.4 kg of water and aged at 50 캜 for 1 hour as it was to obtain a raw material combination solution (III).

(Spray drying of the raw material combination liquid obtained in the combination tank)

Before the completion of the combination of the raw material combination liquid (III), hot air of 50 ° C adjusted to a feed rate of 80 kg / Hr and air heated to 210 ° C was supplied to the centrifugal spray dryer, Lt; / RTI >

The supply amount of the raw material combination liquid to be supplied to the spray dryer was adjusted so that the outlet temperature of the spray dryer was not changed, and the supply amount was 100 kg / Hr. In the meantime, the outlet temperature was 120 ± 5 ° C and there was no significant variation.

(Measurement of ultraviolet visible spectrum)

The obtained dried product was sampled every day, and 0.5 g of the obtained 10 sample products was measured by a diffuse reflection method in a range of 200 to 800 nm using JASCO UV / VIS Spectrometer V-650 manufactured by Nihon Bunko Co., Ltd. Spectralon manufactured by Labspere was used as a standard material for the baseline. The maximum absorbance was 1.02. The absorbance at 600 nm was 0.31 to 0.36, which was the absorbance with which high performance could be expected with reference to the description of JP-A-2009-148749. Therefore, the obtained spray dried product was used for classification operation without sorting.

(Classification operation)

The dried product thus obtained was classified using a sieve having a sieve size of 25 mu m to obtain a powder. The content of the particles of 25 mu m or less in the obtained powder was 0.8 mass% and the average particle diameter was 55 mu m.

(Firing of powder)

And fired in the same manner as in Example 2. [

(Composition of oxide catalyst)

As a result of analyzing the composition of the oxide catalyst, the composition of the metal oxide was MoV _0.21 Nb _0.09 Sb _0.20 W _0.003 Bi _0.004 Ce _0.01 . The amount of silica supported was 47 mass% with respect to the total mass of the catalyst composed of the metal oxide and silica.

(Measurement of specific surface area)

As a result of measurement by the same method as in Example 1, the specific surface area was 13.3 m < 2 > / g.

(Removal of the stone body)

Was removed in the same manner as in Example 1.

(Total pore volume)

As a result of measurement by the same method as in Example 1, the total pore volume was 0.313 cm 3 / g.

(Pore distribution)

As a result of measurement by the same method as in Example 1, the ratio of the pore volume of the pores having a pore diameter of less than 60 nm was 7.3%, and the ratio of the pore volume of the pores having a pore diameter of 120 nm or more was 0.8%.

(Calculation of average pore diameter)

As a result of measurement by the same method as in Example 1, the average pore diameter was 94 nm.

(Measurement of crystallite size)

As a result of measurement by the same method as in Example 1, the crystallite size was 103 nm.

(Ammoxidation reaction of propane)

Using the oxide catalyst obtained above, propane was provided for the vapor-phase ammoxidation reaction by the following method. A mixed gas of propane: ammonia: oxygen: helium = 1: 1: 3: 18 in a molar ratio of propane: ammonia: oxygen: helium = 1 was prepared under a reaction pressure of 440 ° C at a reaction temperature of 440 ° C. Contact time 2.8 (sec · g / cc). After the reaction, the conversion of propane was 88.8%, the yield of acrylonitrile was 54.6%, and the combustion rate of ammonia was 19.2%.

(Example 8)

(Crude solution of niobium raw material liquid)

The liquid was adjusted in the same manner as in Example 1.

(Combination of raw material combination liquid in the combination tank)

To 100 kg of water were added 19.9 kg of ammonium heptamolybdate [(NH ₄ ) ₆ Mo ₇ O ₂₄ .4H ₂ O], 2.75 kg of ammonium metavanadate [NH ₄ VO ₃ ], 2,000 g of antimony trioxide [Sb ₂ O ₃ ] And a cerium nitrate aqueous solution prepared by dissolving 3.27 kg of cerium nitrate [Ce (NO ₃ ) ₃ .6H ₂ O] and 347 g of lanthanum nitrate [La (NO ₃ ) ₃ .6H ₂ O] in 2 kg of water And heated at 95 DEG C for 1 hour while stirring to obtain a raw material combination solution (I).

To 15.95 kg of the raw niobium solution was added 2.28 kg of hydrogen peroxide solution containing 30 mass% as H ₂ O ₂ . The liquid temperature was maintained at approximately 20 占 폚 and stirred and mixed to obtain a raw material combination solution (II).

After cooling the obtained raw material combination solution (I) to 70 캜, 31.0 kg of silica sol containing 30.2% by mass of SiO ₂ and having an average primary particle diameter of 50 nm and 30.0% by mass of SiO ₂ and having an average primary particle diameter 7.70 kg of 18 nm silica sol was added. Subsequently, 3.80 kg of hydrogen peroxide aqueous solution containing 30% by mass of H ₂ O ₂ was added and stirred and mixed at 55 ° C for 30 minutes. Thereafter, 516 g (50% purity) of the raw material combination solution (II) and an aqueous ammonium metatungstate solution Was added. Further, 8.60 kg of powdered silica was dispersed in 77.4 kg of water and aged at 50 캜 for 1 hour as it was to obtain a raw material combination solution (III).

(Spray drying of the raw material combination liquid obtained in the combination tank)

Before the completion of the combination of the raw material combination liquid (III), hot air of 50 ° C adjusted to a feed rate of 80 kg / Hr and air heated to 210 ° C was supplied to the centrifugal spray dryer, Lt; / RTI >

The supply amount of the raw material combination liquid to be supplied to the spray dryer was adjusted so that the outlet temperature of the spray dryer was not changed, and the supply amount was 100 kg / Hr. In the meantime, the outlet temperature was 120 ± 5 ° C and there was no significant variation.

(Measurement of ultraviolet visible spectrum)

The obtained dried product was sampled every day, and 0.5 g of the obtained 10 sample products was measured by a diffuse reflection method in a range of 200 to 800 nm using JASCO UV / VIS Spectrometer V-650 manufactured by Nihon Bunko Co., Ltd. Spectralon manufactured by Labspere was used as a standard material for the baseline. The maximum absorbance was 1.02. The absorbance at 600 nm was 0.31 to 0.36, which was the absorbance with which high performance could be expected with reference to the description of JP-A-2009-148749. Therefore, the obtained spray dried product was used for classification operation without sorting.

(Classification operation)

The dried product thus obtained was classified using a sieve having a sieve size of 25 mu m to obtain a powder. The content of the particles of 25 mu m or less in the obtained powder was 0.8 mass% and the average particle diameter was 55 mu m.

(Firing of powder)

And fired in the same manner as in Example 2. [

(Composition of oxide catalyst)

As a result of analyzing the composition of the oxide catalyst, the composition of the metal oxide was MoV _0.21 Nb _0.09 Sb _0.20 W _0.01 Ce _0.007 La _0.003 . The amount of silica supported was 47 mass% with respect to the total mass of the catalyst composed of the metal oxide and silica.

(Measurement of specific surface area)

As a result of measurement by the same method as in Example 1, the specific surface area was 14.2 m 2 / g.

(Removal of the stone body)

Was removed in the same manner as in Example 1.

(Total pore volume)

As a result of measurement by the same method as in Example 1, the total pore volume was 0.320 cm 3 / g.

(Pore distribution)

The ratio of the pore volume of the pores having a pore diameter of less than 60 nm was 6.7%, and the ratio of the pore volume of the pores having a pore diameter of 120 nm or more was 0.4%.

(Calculation of average pore diameter)

As a result of measurement by the same method as in Example 1, the average pore diameter was 90 nm.

(Measurement of crystallite size)

As a result of measurement by the same method as in Example 1, the crystallite size was 95 nm.

(Ammoxidation reaction of propane)

Using the oxide catalyst obtained above, propane was provided for the vapor-phase ammoxidation reaction by the following method. A mixed gas of propane: ammonia: oxygen: helium = 1: 1: 3: 18 in a molar ratio of propane: ammonia: oxygen: helium = 1 was prepared under a reaction pressure of 440 ° C at a reaction temperature of 440 ° C. Contact time 2.8 (sec · g / cc). After the reaction, the conversion of propane was 88.8%, the yield of acrylonitrile was 54.6%, and the combustion rate of ammonia was 18.8%.

(Example 9)

(Crude solution of niobium raw material liquid)

The liquid was adjusted in the same manner as in Example 1.

(Combination of raw material combination liquid in the combination tank)

To 100 kg of water were added 19.9 kg of ammonium heptamolybdate [(NH ₄ ) ₆ Mo ₇ O ₂₄ .4H ₂ O], 2.75 kg of ammonium metavanadate [NH ₄ VO ₃ ], 2,000 g of antimony trioxide [Sb ₂ O ₃ ] 3.28 kg of cerium nitrate, and a cerium nitrate aqueous solution in which 397 g of cerium nitrate [Ce (NO ₃ ) ₃ .6H ₂ O] and 87 g of yttrium nitrate [Y (NO ₃ ) ₃ .6H ₂ O] And heated at 95 DEG C for 1 hour while stirring to obtain a raw material combination solution (I).

To 15.95 kg of the raw niobium solution was added 2.28 kg of hydrogen peroxide solution containing 30 mass% as H ₂ O ₂ . The liquid temperature was maintained at approximately 20 占 폚 and stirred and mixed to obtain a raw material combination solution (II).

After cooling the obtained raw material combination solution (I) to 70 캜, 31.0 kg of silica sol containing 30.2% by mass of SiO ₂ and having an average primary particle diameter of 50 nm and 30.0% by mass of SiO ₂ and having an average primary particle diameter 7.70 kg of 18 nm silica sol was added. Then, 3.80 kg of hydrogen peroxide aqueous solution containing 30% by mass of H ₂ O ₂ was added and stirred at 55 ° C for 30 minutes. Then 516 g (50% purity) of the raw material combination solution (II) and the aqueous ammonium metatungstate solution were added, ). Further, 8.60 kg of powdered silica was dispersed in 77.4 kg of water and aged at 50 캜 for 1 hour as it was to obtain a raw material combination solution (III).

(Spray drying of the raw material combination liquid obtained in the combination tank)

Before the completion of the combination of the raw material combination liquid (III), hot air of 50 ° C adjusted to a feed rate of 80 kg / Hr and air heated to 210 ° C was supplied to the centrifugal spray dryer, Lt; / RTI >

The supply amount of the raw material combination liquid to be supplied to the spray dryer was adjusted so that the outlet temperature of the spray dryer was not changed, and the supply amount was 100 kg / Hr. In the meantime, the outlet temperature was 120 ± 5 ° C and there was no significant variation.

(Measurement of ultraviolet visible spectrum)

The obtained dried product was sampled every day, and 0.5 g of the obtained 10 sample products was measured by a diffuse reflection method in a range of 200 to 800 nm using JASCO UV / VIS Spectrometer V-650 manufactured by Nihon Bunko Co., Ltd. Spectralon manufactured by Labspere was used as a standard material for the baseline. The maximum absorbance was 1.02. The absorbance at 600 nm was 0.31 to 0.36, which was the absorbance with which high performance could be expected with reference to the description of JP-A-2009-148749. Therefore, the obtained spray dried product was used for classification operation without sorting.

(Classification operation)

The dried product thus obtained was classified using a sieve having a sieve size of 25 mu m to obtain a powder. The content of the particles of 25 mu m or less in the obtained powder was 0.8 mass% and the average particle diameter was 55 mu m.

(Firing of powder)

And fired in the same manner as in Example 2. [

(Composition of oxide catalyst)

As a result of analyzing the composition of the oxide catalyst, the composition of the metal oxide was MoV _0.21 Nb _0.09 Sb _0.20 W _0.01 Ce _0.008 Y _0.002 . The amount of silica supported was 47 mass% with respect to the total mass of the catalyst composed of the metal oxide and silica.

(Measurement of specific surface area)

As a result of measurement by the same method as in Example 1, the specific surface area was 14.5 m 2 / g.

(Removal of the stone body)

Was removed in the same manner as in Example 1.

(Total pore volume)

As a result of measurement by the same method as in Example 1, the total pore volume was 0.330 cm 3 / g.

(Pore distribution)

As a result of measurement by the same method as in Example 1, the ratio of the pore volume of the pores having a pore diameter of less than 60 nm was 7.2%, and the ratio of the pore volume of the pores having a pore diameter of 120 nm or more was 0.5%.

(Calculation of average pore diameter)

As a result of measurement by the same method as in Example 1, the average pore diameter was 91 nm.

(Measurement of crystallite size)

As a result of measurement by the same method as in Example 1, the crystallite size was 102 nm.

(Ammoxidation reaction of propane)

Using the oxide catalyst obtained above, propane was provided for the vapor-phase ammoxidation reaction by the following method. A mixed gas of propane: ammonia: oxygen: helium = 1: 1: 3: 18 in a molar ratio of propane: ammonia: oxygen: helium = 1 was prepared under a reaction pressure of 440 ° C at a reaction temperature of 440 ° C. Contact time 2.8 (sec · g / cc). After the reaction, the conversion of propane was 88.8%, the yield of acrylonitrile was 54.7%, and the combustion rate of ammonia was 18.9%.

(Example 10)

(Crude solution of niobium raw material liquid)

The liquid was adjusted in the same manner as in Example 1.

(Combination of raw material combination liquid in the combination tank)

To 100 kg of water were added 19.9 kg of ammonium heptamolybdate [(NH ₄ ) ₆ Mo ₇ O ₂₄ .4H ₂ O], 2.75 kg of ammonium metavanadate [NH ₄ VO ₃ ], 2,000 g of antimony trioxide [Sb ₂ O ₃ ] Was added 3.28 kg of a cerium nitrate solution and an aqueous cerium nitrate solution in which 297 g of cerium nitrate [Ce (NO ₃ ) ₃ .6H ₂ O] and 146 g of ytterbium nitrate Yb (NO ₃ ) ₃ .4H ₂ O were dissolved in 2 kg of water And heated at 95 DEG C for 1 hour while stirring to obtain a raw material combination solution (I).

To 15.95 kg of the raw niobium solution was added 2.28 kg of hydrogen peroxide solution containing 30 mass% as H ₂ O ₂ . The liquid temperature was maintained at approximately 20 占 폚 and stirred and mixed to obtain a raw material combination solution (II).

After cooling the obtained raw material combination solution (I) to 70 캜, 31.0 kg of silica sol containing 30.2% by mass of SiO ₂ and having an average primary particle diameter of 50 nm and 30.0% by mass of SiO ₂ and having an average primary particle diameter 6.80 kg of 18 nm silica sol was added. Subsequently, 3.80 kg of hydrogen peroxide aqueous solution containing 30% by mass of H ₂ O ₂ was added and stirred and mixed at 55 ° C for 30 minutes. Thereafter, 516 g (50% purity) of the raw material combination solution (II) and an aqueous ammonium metatungstate solution Was added. Further, 8.60 kg of powdered silica was dispersed in 77.4 kg of water and aged at 50 캜 for 1 hour as it was to obtain a raw material combination solution (III).

(Spray drying of the raw material combination liquid obtained in the combination tank)

Before the completion of the combination of the raw material combination liquid (III), hot air of 50 ° C adjusted to a feed rate of 80 kg / Hr and air heated to 210 ° C was supplied to the centrifugal spray dryer, Lt; / RTI >

The supply amount of the raw material combination liquid to be supplied to the spray dryer was adjusted so that the outlet temperature of the spray dryer was not changed, and the supply amount was 100 kg / Hr. In the meantime, the outlet temperature was 120 ± 5 ° C and there was no significant variation.

(Measurement of ultraviolet visible spectrum)

The obtained dried product was sampled every day, and 0.5 g of the obtained 10 sample products was measured by a diffuse reflection method in a range of 200 to 800 nm using JASCO UV / VIS Spectrometer V-650 manufactured by Nihon Bunko Co., Ltd. Spectralon manufactured by Labspere was used as a standard material for the baseline. The maximum absorbance was 1.02. The absorbance at 600 nm was 0.31 to 0.36, which was the absorbance with which high performance could be expected with reference to the description of JP-A-2009-148749. Therefore, the obtained spray dried product was used for classification operation without sorting.

(Classification operation)

The dried product thus obtained was classified using a sieve having a sieve size of 25 mu m to obtain a powder. The content of the particles of 25 mu m or less in the obtained powder was 0.8 mass% and the average particle diameter was 55 mu m.

(Firing of powder)

And fired in the same manner as in Example 2. [

(Composition of oxide catalyst)

As a result of analyzing the composition of the oxide catalyst, the composition of the metal oxide was MoV _0.21 Nb _0.09 Sb _0.20 W _0.01 Ce _0.006 Yb _0.003 . The amount of silica supported was 47 mass% with respect to the total mass of the catalyst composed of the metal oxide and silica.

(Measurement of specific surface area)

As a result of measurement by the same method as in Example 1, the specific surface area was 15.2 m 2 / g.

(Removal of the stone body)

Was removed in the same manner as in Example 1.

(Total pore volume)

As a result of measurement by the same method as in Example 1, the total pore volume was 0.334 cm 3 / g.

(Pore distribution)

As a result, the ratio of the pore volume of pores having a pore diameter of less than 60 nm was 8.2%, and the ratio of pore volume of pores having a pore diameter of 120 nm or more was 0.4%.

(Calculation of average pore diameter)

As a result of measurement by the same method as in Example 1, the average pore diameter was 88 nm.

(Measurement of crystallite size)

As a result of measurement by the same method as in Example 1, the crystallite size was 98 nm.

(Ammoxidation reaction of propane)

Using the oxide catalyst obtained above, propane was provided for the vapor-phase ammoxidation reaction by the following method. A mixed gas of propane: ammonia: oxygen: helium = 1: 1: 3: 18 in a molar ratio of propane: ammonia: oxygen: helium = 1 was prepared under a reaction pressure of 440 ° C at a reaction temperature of 440 ° C. Contact time 2.8 (sec · g / cc). The propane conversion rate after the reaction was 88.8%, the acrylonitrile yield was 54.6%, and the ammonia combustion rate was 19.0%.

(Example 11)

(Crude solution of niobium raw material liquid)

The liquid was adjusted in the same manner as in Example 1.

(Combination of raw material combination liquid in the combination tank)

To 100 kg of water were added 19.9 kg of ammonium heptamolybdate [(NH ₄ ) ₆ Mo ₇ O ₂₄ .4H ₂ O], 2.75 kg of ammonium metavanadate [NH ₄ VO ₃ ], 2,000 g of antimony trioxide [Sb ₂ O ₃ ] , 3.25 kg of cerium nitrate [Ce (NO ₃ ) ₃ .6H ₂ O] and 495 g of cerium nitrate [Ce (NO ₃ ) ₃ .6H ₂ O] were dissolved in 2 kg of water and heated at 95 ° C for 1 hour with stirring to obtain a raw material combination solution .

To 15.95 kg of the raw niobium solution was added 2.28 kg of hydrogen peroxide solution containing 30 mass% as H ₂ O ₂ . The liquid temperature was maintained at approximately 20 占 폚 and stirred and mixed to obtain a raw material combination solution (II).

Obtained after cooling the material combination solution (I) to 70 ℃, SiO ₂ average primary particle diameter with a sol having an average primary particle diameter of 23 nm containing a 30.2 wt% silica 31.0 kg, containing 30.0% by mass as SiO ₂ as a 6.80 kg of 13 nm silica sol was added. Then, 3.80 kg of hydrogen peroxide aqueous solution containing 30% by mass of H ₂ O ₂ was added and stirred at 55 ° C for 30 minutes. Then 516 g (50% purity) of the raw material combination solution (II) and the aqueous ammonium metatungstate solution were added, ). Further, 8.60 kg of powdered silica was dispersed in 77.4 kg of water and aged at 50 캜 for 1 hour as it was to obtain a raw material combination solution (III).

(Spray drying of the raw material combination liquid obtained in the combination tank)

Before the completion of the combination of the raw material combination liquid (III), hot air of 50 ° C adjusted to a feed rate of 80 kg / Hr and air heated to 210 ° C was supplied to the centrifugal spray dryer, Lt; / RTI >

The supply amount of the raw material combination liquid to be supplied to the spray dryer was adjusted so that the outlet temperature of the spray dryer was not changed, and the supply amount was 100 kg / Hr. In the meantime, the outlet temperature was 120 ± 5 ° C and there was no significant variation.

(Measurement of ultraviolet visible spectrum)

The obtained dried product was sampled every day, and 0.5 g of the obtained 10 sample products was measured by a diffuse reflection method in a range of 200 to 800 nm using JASCO UV / VIS Spectrometer V-650 manufactured by Nihon Bunko Co., Ltd. Spectralon manufactured by Labspere was used as a standard material for the baseline. The maximum absorbance was 1.02. The absorbance at 600 nm was 0.31 to 0.36, which was the absorbance with which high performance could be expected with reference to the description of JP-A-2009-148749. Therefore, the obtained spray dried product was used for classification operation without sorting.

(Classification operation)

The dried product thus obtained was classified using a sieve having a sieve size of 25 mu m to obtain a powder. The content of the particles of 25 mu m or less in the obtained powder was 0.8 mass% and the average particle diameter was 55 mu m.

(Firing of powder)

Seven slabs each having a height of 150 mm in a cylindrical sintered tube made of SUS having an inner diameter of 500 mm, a length of 3500 mm and a thickness of 20 mm were set so as to divide the length of the heating furnace into eight equal parts at a rate of 20 kg / hr And heated to 370 캜 for about 4 hours while rotating the fired tube at 4 rpm under a nitrogen gas flow of 600 N 터 l / min and heated to a heating furnace temperature of 370 캜 for 3 hours, And a shear fired product was obtained by shearing firing. Seven slabs each having a height of 150 mm in an SUS-made sintered pipe having an inner diameter of 500 mm, a length of 3500 mm and a thickness of 20 mm were installed so as to divide the length of the heating furnace into 8 equal parts. The sintering tube was rotated at 4 rpm , And shear debris was distributed at a rate of 15 kg / hr. At that time, with a hammering device provided with a hammer having a mass of 14 kg, which is made of stainless steel and the tip of the striking part was provided, the portion of the sintered tube on the powder introduction side (the portion not covered with the heating furnace) A temperature profile at which the temperature was raised to 680 캜 at a rate of 2 캜 / min under a nitrogen gas flow of 500 N / min while being blown once at a rate of 5 캜 / The temperature of the furnace was adjusted so that the oxide catalyst was obtained.

(Composition of oxide catalyst)

As a result of analyzing the composition of the oxide catalyst, the composition ratio of the metal oxide was MoV _0.21 Nb _0.09 Sb _0.20 W _0.01 Ce _0.01 . The amount of silica supported was 47 mass% with respect to the total mass of the catalyst composed of the metal oxide and silica.

(Measurement of specific surface area)

As a result of measurement by the same method as in Example 1, the specific surface area was 14.6 m 2 / g.

(Removal of the stone body)

Was removed in the same manner as in Example 1.

(Total pore volume)

As a result of measurement by the same method as in Example 1, the total pore volume was 0.350 cm 3 / g.

(Pore distribution)

The ratio of the pore volume of the pores having a pore diameter of less than 60 nm was 5.8%, and the ratio of the pore volume of the pores having a pore diameter of 120 nm or more was 0.9%.

(Calculation of average pore diameter)

As a result of measurement by the same method as in Example 1, the average pore diameter was 96 nm.

(Measurement of crystallite size)

As a result of measurement by the same method as in Example 1, the crystallite size was 61 nm.

(Ammoxidation reaction of propane)

Using the oxide catalyst obtained above, propane was provided for the vapor-phase ammoxidation reaction by the following method. A mixed gas of propane: ammonia: oxygen: helium = 1: 1: 3: 18 in a molar ratio of propane: ammonia: oxygen: helium = 1 was prepared under a reaction pressure of 440 ° C at a reaction temperature of 440 ° C. Contact time 2.8 (sec · g / cc). After the reaction, the conversion of propane was 88.9%, the yield of acrylonitrile was 54.4%, and the combustion rate of ammonia was 19.1%.

(Example 12)

(Crude solution of niobium raw material liquid)

The liquid was adjusted in the same manner as in Example 1.

(Combination of raw material combination liquid in the combination tank)

To 100 kg of water were added 19.9 kg of ammonium heptamolybdate [(NH ₄ ) ₆ Mo ₇ O ₂₄ .4H ₂ O], 2.75 kg of ammonium metavanadate [NH ₄ VO ₃ ], 2,000 g of antimony trioxide [Sb ₂ O ₃ ] , 3.25 kg of cerium nitrate [Ce (NO ₃ ) ₃ .6H ₂ O] and 495 g of cerium nitrate [Ce (NO ₃ ) ₃ .6H ₂ O] were dissolved in 2 kg of water and heated at 95 ° C for 1 hour with stirring to obtain a raw material combination solution .

To 15.95 kg of the raw niobium solution was added 2.28 kg of hydrogen peroxide solution containing 30 mass% as H ₂ O ₂ . The liquid temperature was maintained at approximately 20 占 폚 and stirred and mixed to obtain a raw material combination solution (II).

Obtained after cooling the material combination solution (I) to 70 ℃, SiO ₂ average primary particle diameter with a sol having an average primary particle diameter of 23 nm containing a 30.2 wt% silica 31.0 kg, containing 30.0% by mass as SiO ₂ as a 6.80 kg of 13 nm silica sol was added. Then, 3.80 kg of hydrogen peroxide aqueous solution containing 30% by mass of H ₂ O ₂ was added and stirred at 55 ° C for 30 minutes. Then 516 g (50% purity) of the raw material combination solution (II) and the aqueous ammonium metatungstate solution were added, ). Further, 8.60 kg of powdered silica was dispersed in 77.4 kg of water and aged at 50 캜 for 1 hour as it was to obtain a raw material combination solution (III).

(Spray drying of the raw material combination liquid obtained in the combination tank)

Before the completion of the combination of the raw material combination liquid (III), hot air of 50 ° C adjusted to a feed rate of 80 kg / Hr and air heated to 210 ° C was supplied to the centrifugal spray dryer, Lt; / RTI >

The supply amount of the raw material combination liquid to be supplied to the spray dryer was adjusted so that the outlet temperature of the spray dryer was not changed, and the supply amount was 100 kg / Hr. In the meantime, the outlet temperature was 120 ± 5 ° C and there was no significant variation.

(Measurement of ultraviolet visible spectrum)

The obtained dried product was sampled every day, and 0.5 g of the obtained 10 sample products was measured by a diffuse reflection method in a range of 200 to 800 nm using JASCO UV / VIS Spectrometer V-650 manufactured by Nihon Bunko Co., Ltd. Spectralon manufactured by Labspere was used as a standard material for the baseline. The maximum absorbance was 1.02. The absorbance at 600 nm was 0.31 to 0.36, which was the absorbance with which high performance could be expected with reference to the description of JP-A-2009-148749. Therefore, the obtained spray dried product was used for classification operation without sorting.

(Classification operation)

The dried product thus obtained was classified using a sieve having a sieve size of 25 mu m to obtain a powder. The content of the particles of 25 mu m or less in the obtained powder was 0.8 mass% and the average particle diameter was 55 mu m.

(Firing of powder)

Seven slabs each having a height of 150 mm in a cylindrical sintered tube made of SUS having an inner diameter of 500 mm, a length of 3500 mm and a thickness of 20 mm were set so as to divide the length of the heating furnace into eight equal parts at a rate of 20 kg / hr And heated to 370 캜 for about 4 hours while rotating the fired tube at 4 rpm under a nitrogen gas flow of 600 N 터 l / min and heated to a heating furnace temperature of 370 캜 for 3 hours, And a shear fired product was obtained by shearing firing. Seven slabs each having a height of 150 mm in an SUS-made sintered pipe having an inner diameter of 500 mm, a length of 3500 mm and a thickness of 20 mm were installed so as to divide the length of the heating furnace into 8 equal parts. The sintering tube was rotated at 4 rpm , And shear debris was distributed at a rate of 15 kg / hr. At that time, with a hammering device provided with a hammer having a mass of 14 kg, which is made of stainless steel and the tip of the striking part was provided, the portion of the sintered tube on the powder introduction side (the portion not covered with the heating furnace) The temperature profile was raised to 685 DEG C at a rate of 2 DEG C / min under nitrogen gas flow of 500 N / min while being blown once at a rate of 5 seconds from the height, and baked at 685 DEG C for 2.5 hours, The temperature of the furnace was adjusted so that the oxide catalyst was obtained.

(Composition of oxide catalyst)

As a result of analyzing the composition of the oxide catalyst, the composition of the metal oxide was MoV _0.21 Nb _0.09 Sb _0.20 W _0.01 Ce _0.01 . The amount of silica supported was 47 mass% with respect to the total mass of the catalyst composed of the metal oxide and silica.

(Measurement of specific surface area)

As a result of measurement by the same method as in Example 1, the specific surface area was 15.1 m < 2 > / g.

(Removal of the stone body)

Was removed in the same manner as in Example 1.

(Total pore volume)

As a result of measurement by the same method as in Example 1, the total pore volume was 0.306 cm 3 / g.

(Pore distribution)

As a result of measurement by the same method as in Example 1, the ratio of the pore volume of the pores having a pore diameter of less than 60 nm was 9.3%, and the ratio of the pore volume of the pores having a pore diameter of 120 nm or more was 0.3%.

(Calculation of average pore diameter)

As a result of measurement by the same method as in Example 1, the average pore diameter was 81 nm.

(Measurement of crystallite size)

As a result of measurement by the same method as in Example 1, the crystallite size was 181 nm.

(Ammoxidation reaction of propane)

Using the oxide catalyst obtained above, propane was provided for the vapor-phase ammoxidation reaction by the following method. A mixed gas of propane: ammonia: oxygen: helium = 1: 1: 3: 18 in a molar ratio of propane: ammonia: oxygen: helium = 1 was prepared under a reaction pressure of 440 ° C at a reaction temperature of 440 ° C. Contact time 2.8 (sec · g / cc). After the reaction, the conversion of propane was 89.1%, the yield of acrylonitrile was 54.3%, and the combustion rate of ammonia was 19.4%.

(Example 13)

(Crude solution of niobium raw material liquid)

The liquid was adjusted in the same manner as in Example 1.

(Combination of raw material combination liquid in the combination tank)

To 100 kg of water were added 19.9 kg of ammonium heptamolybdate [(NH ₄ ) ₆ Mo ₇ O ₂₄ .4H ₂ O], 2.75 kg of ammonium metavanadate [NH ₄ VO ₃ ], 2,000 g of antimony trioxide [Sb ₂ O ₃ ] , 3.25 kg of cerium nitrate [Ce (NO ₃ ) ₃ .6H ₂ O] and 495 g of cerium nitrate [Ce (NO ₃ ) ₃ .6H ₂ O] were dissolved in 2 kg of water and heated at 95 ° C for 1 hour with stirring to obtain a raw material combination solution .

To 15.95 kg of the raw niobium solution was added 2.28 kg of hydrogen peroxide solution containing 30 mass% as H ₂ O ₂ . The liquid temperature was maintained at approximately 20 占 폚 and stirred and mixed to obtain a raw material combination solution (II).

After cooling the obtained raw material combination solution (I) to 70 캜, 34.0 kg of silica sol containing 30.2% by mass of SiO ₂ and having an average primary particle diameter of 55 nm and 30.0% by mass of SiO ₂ containing an average primary particle diameter 3.80 kg of 13 nm silica sol was added. Then, 3.80 kg of hydrogen peroxide aqueous solution containing 30% by mass of H ₂ O ₂ was added and stirred at 55 ° C for 30 minutes. Then 516 g (50% purity) of the raw material combination solution (II) and the aqueous ammonium metatungstate solution were added, ). Further, 8.60 kg of powdered silica was dispersed in 77.4 kg of water and aged at 50 캜 for 1 hour as it was to obtain a raw material combination solution (III).

(Spray drying of the raw material combination liquid obtained in the combination tank)

Before the completion of the combination of the raw material combination liquid (III), hot air of 50 ° C adjusted to a feed rate of 80 kg / Hr and air heated to 210 ° C was supplied to the centrifugal spray dryer, Lt; / RTI >

The supply amount of the raw material combination liquid to be supplied to the spray dryer was adjusted so that the outlet temperature of the spray dryer was not changed, and the supply amount was 100 kg / Hr. In the meantime, the outlet temperature was 120 ± 5 ° C and there was no significant variation.

(Measurement of ultraviolet visible spectrum)

The obtained dried product was sampled every day, and 0.5 g of the obtained 10 sample products was measured by a diffuse reflection method in a range of 200 to 800 nm using JASCO UV / VIS Spectrometer V-650 manufactured by Nihon Bunko Co., Ltd. Spectralon manufactured by Labspere was used as a standard material for the baseline. The maximum absorbance was 1.02. The absorbance at 600 nm was 0.31 to 0.36, and when the reference was made to Japanese Patent Application Laid-Open No. 2009-148749, the absorbance was such that high performance could be expected. Therefore, the obtained spray dried product was used for classification operation without sorting.

(Classification operation)

The dried product thus obtained was classified using a sieve having a sieve size of 25 mu m to obtain a powder. The content of the particles of 25 mu m or less in the obtained powder was 0.8 mass% and the average particle diameter was 55 mu m.

(Firing of powder)

Seven slabs each having a height of 150 mm in a cylindrical sintered tube made of SUS having an inner diameter of 500 mm, a length of 3500 mm and a thickness of 20 mm were set so as to divide the length of the heating furnace into eight equal parts at a rate of 20 kg / hr And heated to 370 캜 for about 4 hours while rotating the fired tube at 4 rpm under a nitrogen gas flow of 600 N 터 l / min and heated to a heating furnace temperature of 370 캜 for 3 hours, And a shear fired product was obtained by shearing firing. Seven slabs each having a height of 150 mm in an SUS-made sintered pipe having an inner diameter of 500 mm, a length of 3500 mm and a thickness of 20 mm were installed so as to divide the length of the heating furnace into 8 equal parts. The sintering tube was rotated at 4 rpm , And shear debris was distributed at a rate of 15 kg / hr. At that time, with a hammering device provided with a hammer having a mass of 14 kg, which is made of stainless steel and the tip of the striking part was provided, the portion of the sintered tube on the powder introduction side (the portion not covered with the heating furnace) A temperature profile at which the temperature was raised to 695 캜 at a rate of 2 캜 / min under a nitrogen gas flow of 500 N / min while being blown once at a rate of 5 캜 for 5 seconds and then fired at 695 캜 for 2 hours, The temperature of the furnace was adjusted so that the oxide catalyst was obtained.

(Composition of oxide catalyst)

As a result of analyzing the composition of the oxide catalyst, the composition of the metal oxide was MoV _0.21 Nb _0.09 Sb _0.20 W _0.01 Ce _0.01 . The amount of silica supported was 47 mass% with respect to the total mass of the catalyst composed of the metal oxide and silica.

(Measurement of specific surface area)

As a result of measurement by the same method as in Example 1, the specific surface area was 8.0 m < 2 > / g.

(Removal of the stone body)

Was removed in the same manner as in Example 1.

(Total pore volume)

As a result of measurement by the same method as in Example 1, the total pore volume was 0.168 cm 3 / g.

(Pore distribution)

The ratio of the pore volume of the pores having a pore diameter of less than 60 nm was 8.8%, and the ratio of the pore volume of the pores having a pore diameter of 120 nm or more was 0.4%.

(Calculation of average pore diameter)

As a result of measurement by the same method as in Example 1, the average pore diameter was 84 nm.

(Measurement of crystallite size)

As a result of measurement by the same method as in Example 1, the crystallite size was 156 nm.

(Ammoxidation reaction of propane)

Using the oxide catalyst obtained above, propane was provided for the vapor-phase ammoxidation reaction by the following method. A mixed gas of propane: ammonia: oxygen: helium = 1: 1: 3: 18 in a molar ratio of propane: ammonia: oxygen: helium = 1 was prepared under a reaction pressure of 440 ° C at a reaction temperature of 440 ° C. Contact time 2.8 (sec · g / cc). After the reaction, the conversion of propane was 89.2%, the yield of acrylonitrile was 54.0%, and the combustion rate of ammonia was 19.2%.

(Example 14)

(Crude solution of niobium raw material liquid)

The liquid was adjusted in the same manner as in Example 1.

(Combination of raw material combination liquid in the combination tank)

To 100 kg of water were added 19.9 kg of ammonium heptamolybdate [(NH ₄ ) ₆ Mo ₇ O ₂₄ .4H ₂ O], 2.75 kg of ammonium metavanadate [NH ₄ VO ₃ ], 2,000 g of antimony trioxide [Sb ₂ O ₃ ] , 3.25 kg of cerium nitrate [Ce (NO ₃ ) ₃ .6H ₂ O] and 495 g of cerium nitrate [Ce (NO ₃ ) ₃ .6H ₂ O] were dissolved in 2 kg of water and heated at 95 ° C for 1 hour with stirring to obtain a raw material combination solution .

To 15.95 kg of the raw niobium solution was added 2.28 kg of hydrogen peroxide solution containing 30 mass% as H ₂ O ₂ . The liquid temperature was maintained at approximately 20 占 폚 and stirred and mixed to obtain a raw material combination solution (II).

Obtained after cooling the material combination solution (I) to 70 ℃, SiO ₂ average primary particle diameter with a sol having an average primary particle diameter of 23 nm containing a 30.2 wt% silica 31.0 kg, containing 30.0% by mass as SiO ₂ as a 6.80 kg of 13 nm silica sol was added. Then, 3.80 kg of hydrogen peroxide aqueous solution containing 30% by mass of H ₂ O ₂ was added and stirred at 55 ° C for 30 minutes. Then 516 g (50% purity) of the raw material combination solution (II) and the aqueous ammonium metatungstate solution were added, ). Further, 8.60 kg of powdered silica was dispersed in 77.4 kg of water and aged at 50 캜 for 1 hour as it was to obtain a raw material combination solution (III).

(Spray drying of the raw material combination liquid obtained in the combination tank)

Before the completion of the combination of the raw material combination liquid (III), hot air of 50 ° C adjusted to a feed rate of 80 kg / Hr and air heated to 210 ° C was supplied to the centrifugal spray dryer, Lt; / RTI >

The supply amount of the raw material combination liquid to be supplied to the spray dryer was adjusted so that the outlet temperature of the spray dryer was not changed, and the supply amount was 100 kg / Hr. In the meantime, the outlet temperature was 120 ± 5 ° C and there was no significant variation.

(Measurement of ultraviolet visible spectrum)

The obtained dried product was sampled every day, and 0.5 g of the obtained 10 sample products was measured by a diffuse reflection method in a range of 200 to 800 nm using JASCO UV / VIS Spectrometer V-650 manufactured by Nihon Bunko Co., Ltd. Spectralon manufactured by Labspere was used as a standard material for the baseline. The maximum absorbance was 1.02. The absorbance at 600 nm was 0.31 to 0.36, which was the absorbance with which high performance could be expected with reference to the description of JP-A-2009-148749. Therefore, the obtained spray dried product was used for classification operation without sorting.

(Classification operation)

The dried product thus obtained was classified using a sieve having a sieve size of 25 mu m to obtain a powder. The content of the particles of 25 mu m or less in the obtained powder was 0.8 mass% and the average particle diameter was 55 mu m.

(Firing of powder)

Seven slabs each having a height of 150 mm in a cylindrical sintered tube made of SUS having an inner diameter of 500 mm, a length of 3500 mm and a thickness of 20 mm were set so as to divide the length of the heating furnace into eight equal parts at a rate of 20 kg / hr And heated to 370 캜 for about 4 hours while rotating the fired tube at 4 rpm under a nitrogen gas flow of 600 N 터 l / min and heated to a heating furnace temperature of 370 캜 for 3 hours, And a shear fired product was obtained by shearing firing. Seven slabs each having a height of 150 mm in an SUS-made sintered pipe having an inner diameter of 500 mm, a length of 3500 mm and a thickness of 20 mm were installed so as to divide the length of the heating furnace into 8 equal parts. The sintering tube was rotated at 4 rpm , And shear debris was distributed at a rate of 15 kg / hr. At that time, with a hammering device provided with a hammer having a mass of 14 kg, which is made of stainless steel and the tip of the striking part was provided, the portion of the sintered tube on the powder introduction side (the portion not covered with the heating furnace) A temperature profile at which the temperature was raised to 670 캜 at a rate of 2 캜 / min under a nitrogen gas flow of 500 N / min while being blown once at a rate of 5 캜 for 5 seconds, and then fired at 670 캜 for 2 hours, The temperature of the furnace was adjusted so that the oxide catalyst was obtained.

(Composition of oxide catalyst)

As a result of analyzing the composition of the oxide catalyst, the composition of the metal oxide was MoV _0.21 Nb _0.09 Sb _0.20 W _0.01 Ce _0.01 . The amount of silica supported was 47 mass% with respect to the total mass of the catalyst composed of the metal oxide and silica.

(Measurement of specific surface area)

As a result of measurement by the same method as in Example 1, the specific surface area was found to be 16.7 m < 2 > / g.

(Removal of the stone body)

Was removed in the same manner as in Example 1.

(Total pore volume)

As a result of measurement by the same method as in Example 1, the total pore volume was 0.342 cm 3 / g.

(Pore distribution)

As a result of measurement by the same method as in Example 1, the ratio of the pore volume of the pores having a pore diameter of less than 60 nm was 9.0%, and the ratio of the pore volume of the pores having a pore diameter of 120 nm or more was 0.3%.

(Calculation of average pore diameter)

As a result of measurement by the same method as in Example 1, the average pore diameter was 82 nm.

(Measurement of crystallite size)

As a result of measurement by the same method as in Example 1, the crystallite size was 52 nm.

(Ammoxidation reaction of propane)

Using the oxide catalyst obtained above, propane was provided for the vapor-phase ammoxidation reaction by the following method. A mixed gas of propane: ammonia: oxygen: helium = 1: 1: 3: 18 in a molar ratio of propane: ammonia: oxygen: helium = 1 was prepared under a reaction pressure of 440 ° C at a reaction temperature of 440 ° C. Contact time 2.8 (sec · g / cc). After the reaction, the conversion of propane was 89.1%, the yield of acrylonitrile was 54.0%, and the combustion rate of ammonia was 19.5%.

(Example 15)

(Crude solution of niobium raw material liquid)

The liquid was adjusted in the same manner as in Example 1.

(Combination of raw material combination liquid in the combination tank)

To 100 kg of water were added 19.9 kg of ammonium heptamolybdate [(NH ₄ ) ₆ Mo ₇ O ₂₄ .4H ₂ O], 2.75 kg of ammonium metavanadate [NH ₄ VO ₃ ], 2,000 g of antimony trioxide [Sb ₂ O ₃ ] , 3.25 kg of cerium nitrate [Ce (NO ₃ ) ₃ .6H ₂ O] and 495 g of cerium nitrate [Ce (NO ₃ ) ₃ .6H ₂ O] were dissolved in 2 kg of water and heated at 95 ° C for 1 hour with stirring to obtain a raw material combination solution .

To 15.95 kg of the raw niobium solution was added 2.28 kg of hydrogen peroxide solution containing 30 mass% as H ₂ O ₂ . The liquid temperature was maintained at approximately 20 占 폚 and stirred and mixed to obtain a raw material combination solution (II).

The obtained raw material combination solution (I) After cooling to 70 ℃, SiO ₂ average primary particle diameter of 30.2 and a% by mass of the average primary particle diameter of the sol of 25 nm silica 30.7 kg containing, containing 30.0% by mass as SiO ₂ as a 7.1 kg of 12 nm silica sol was added. Then, 3.80 kg of hydrogen peroxide aqueous solution containing 30% by mass of H ₂ O ₂ was added and stirred at 55 ° C for 30 minutes. Then 516 g (50% purity) of the raw material combination solution (II) and the aqueous ammonium metatungstate solution were added, ). Further, 8.60 kg of powdered silica was dispersed in 77.4 kg of water and aged at 50 캜 for 1 hour as it was to obtain a raw material combination solution (III).

(Spray drying of the raw material combination liquid obtained in the combination tank)

Before the completion of the combination of the raw material combination liquid (III), hot air of 50 ° C adjusted to a feed rate of 80 kg / Hr and air heated to 210 ° C was supplied to the centrifugal spray dryer, Lt; / RTI >

The supply amount of the raw material combination liquid to be supplied to the spray dryer was adjusted so that the outlet temperature of the spray dryer was not changed, and the supply amount was 100 kg / Hr. In the meantime, the outlet temperature was 120 ± 5 ° C and there was no significant variation.

(Measurement of ultraviolet visible spectrum)

The obtained dried product was sampled every day, and 0.5 g of the obtained 10 sample products was measured by a diffuse reflection method in a range of 200 to 800 nm using JASCO UV / VIS Spectrometer V-650 manufactured by Nihon Bunko Co., Ltd. Spectralon manufactured by Labspere was used as a standard material for the baseline. The maximum absorbance was 1.02. The absorbance at 600 nm was 0.31 to 0.36, which was the absorbance with which high performance could be expected with reference to the description of JP-A-2009-148749. Therefore, the obtained spray dried product was used for classification operation without sorting.

(Classification operation)

The dried product thus obtained was classified using a sieve having a sieve size of 25 mu m to obtain a powder. The content of the particles of 25 mu m or less in the obtained powder was 0.8 mass% and the average particle diameter was 55 mu m.

(Firing of powder)

Seven slabs each having a height of 150 mm in a cylindrical sintered tube made of SUS having an inner diameter of 500 mm, a length of 3500 mm and a thickness of 20 mm were set so as to divide the length of the heating furnace into eight equal parts at a rate of 20 kg / hr And heated to 370 캜 for about 4 hours while rotating the fired tube at 4 rpm under a nitrogen gas flow of 600 N 터 l / min and heated to a heating furnace temperature of 370 캜 for 3 hours, And a shear fired product was obtained by shearing firing. Seven slabs each having a height of 150 mm in an SUS-made sintered pipe having an inner diameter of 500 mm, a length of 3500 mm and a thickness of 20 mm were installed so as to divide the length of the heating furnace into 8 equal parts. The sintering tube was rotated at 4 rpm , And shear debris was distributed at a rate of 15 kg / hr. At that time, with a hammering device provided with a hammer having a mass of 14 kg, which is made of stainless steel and the tip of the striking part was provided, was placed in the powder introduction side portion (the portion not covered with the heating furnace) A temperature profile at which the temperature was raised to 695 캜 at a rate of 2 캜 / min under a nitrogen gas flow of 500 N / min while being blown once at a rate of 5 캜 / The temperature of the furnace was adjusted so that the oxide catalyst was obtained.

(Composition of oxide catalyst)

As a result of analyzing the composition of the oxide catalyst, the composition of the metal oxide was MoV _0.21 Nb _0.09 Sb _0.20 W _0.01 Ce _0.01 . The amount of silica supported was 47 mass% with respect to the total mass of the catalyst composed of the metal oxide and silica.

(Measurement of specific surface area)

As a result of measurement by the same method as in Example 1, the specific surface area was 9.2 m < 2 > / g.

(Removal of the stone body)

Was removed in the same manner as in Example 1.

(Total pore volume)

As a result of measurement by the same method as in Example 1, the total pore volume was 0.170 cm 3 / g.

(Pore distribution)

The ratio of the pore volume of the pores having a pore diameter of less than 60 nm was 10.6%, and the ratio of the pore volume of the pores having a pore diameter of 120 nm or more was 0.3%.

(Calculation of average pore diameter)

As a result of measurement by the same method as in Example 1, the average pore diameter was 74 nm.

(Measurement of crystallite size)

As a result of measurement by the same method as in Example 1, the crystallite size was 55 nm.

(Ammoxidation reaction of propane)

Using the oxide catalyst obtained above, propane was provided for the vapor-phase ammoxidation reaction by the following method. A mixed gas of propane: ammonia: oxygen: helium = 1: 1: 3: 18 in a molar ratio of propane: ammonia: oxygen: helium = 1 was prepared under a reaction pressure of 440 ° C at a reaction temperature of 440 ° C. Contact time 2.8 (sec · g / cc). After the reaction, the conversion of propane was 89.1%, the yield of acrylonitrile was 54.1%, and the combustion rate of ammonia was 19.3%.

(Example 16)

(Crude solution of niobium raw material liquid)

The liquid was adjusted in the same manner as in Example 1.

(Combination of raw material combination liquid in the combination tank)

To 100 kg of water were added 19.9 kg of ammonium heptamolybdate [(NH ₄ ) ₆ Mo ₇ O ₂₄ .4H ₂ O], 2.75 kg of ammonium metavanadate [NH ₄ VO ₃ ], 2,000 g of antimony trioxide [Sb ₂ O ₃ ] , 3.25 kg of cerium nitrate [Ce (NO ₃ ) ₃ .6H ₂ O] and 495 g of cerium nitrate [Ce (NO ₃ ) ₃ .6H ₂ O] were dissolved in 2 kg of water and heated at 95 ° C for 1 hour with stirring to obtain a raw material combination solution .

To 15.95 kg of the raw niobium solution was added 2.28 kg of hydrogen peroxide solution containing 30 mass% as H ₂ O ₂ . The liquid temperature was maintained at approximately 20 占 폚 and stirred and mixed to obtain a raw material combination solution (II).

Obtained after cooling the material combination solution (I) to 70 ℃, SiO ₂ average primary particle diameter with a sol having an average primary particle diameter of 23 nm containing a 30.2 wt% silica 56.4 kg, containing 30.0% by mass as SiO ₂ as a 6.90 kg of 13 nm silica sol was added. Then, 3.80 kg of hydrogen peroxide aqueous solution containing 30% by mass of H ₂ O ₂ was added and stirred at 55 ° C for 30 minutes. Then 516 g (50% purity) of the raw material combination solution (II) and the aqueous ammonium metatungstate solution were added, ). Thereafter, the mixture was aged at 50 DEG C for 1 hour to obtain a raw material combination solution (III).

(Spray drying of the raw material combination liquid obtained in the combination tank)

Before the completion of the combination of the raw material combination liquid (III), hot air of 50 ° C adjusted to a feed rate of 80 kg / Hr and air heated to 210 ° C was supplied to the centrifugal spray dryer, Lt; / RTI >

The supply amount of the raw material combination liquid to be supplied to the spray dryer was adjusted so that the outlet temperature of the spray dryer was not changed, and the supply amount was 100 kg / Hr. In the meantime, the outlet temperature was 120 ± 5 ° C and there was no significant variation.

(Measurement of ultraviolet visible spectrum)

The obtained dried product was sampled every day, and 0.5 g of the obtained 10 sample products was measured by a diffuse reflection method in a range of 200 to 800 nm using JASCO UV / VIS Spectrometer V-650 manufactured by Nihon Bunko Co., Ltd. Spectralon manufactured by Labspere was used as a standard material for the baseline. The maximum absorbance was 1.02. The absorbance at 600 nm was 0.31 to 0.36, which was the absorbance with which high performance could be expected with reference to the description of JP-A-2009-148749. Therefore, the obtained spray dried product was used for classification operation without sorting.

(Classification operation)

The dried product thus obtained was classified using a sieve having a sieve size of 25 mu m to obtain a powder. The content of the particles of 25 mu m or less in the obtained powder was 0.8 mass% and the average particle diameter was 55 mu m.

(Firing of powder)

Seven slabs each having a height of 150 mm in a cylindrical sintered tube made of SUS having an inner diameter of 500 mm, a length of 3500 mm and a thickness of 20 mm were set so as to divide the length of the heating furnace into eight equal parts at a rate of 20 kg / hr And heated to 370 캜 for about 4 hours while rotating the fired tube at 4 rpm under a nitrogen gas flow of 600 N 터 l / min and heated to a heating furnace temperature of 370 캜 for 3 hours, And a shear fired product was obtained by shearing firing. Seven slabs each having a height of 150 mm in an SUS-made sintered pipe having an inner diameter of 500 mm, a length of 3500 mm and a thickness of 20 mm were installed so as to divide the length of the heating furnace into 8 equal parts. The sintering tube was rotated at 4 rpm , And shear debris was distributed at a rate of 15 kg / hr. At that time, with a hammering device provided with a hammer having a mass of 14 kg, which is made of stainless steel and the tip of the striking part was provided, was placed in the powder introduction side portion (the portion not covered with the heating furnace) The temperature profile was obtained by raising the temperature to 685 占 폚 at 2 占 폚 / min under nitrogen gas flow of 500 N / min while blowing once at 5 seconds from the height for 1 hour at 68 占 폚 for 2 hours, The temperature of the furnace was adjusted so that the oxide catalyst was obtained.

(Composition of oxide catalyst)

As a result of analyzing the composition of the oxide catalyst, the composition of the metal oxide was MoV _0.21 Nb _0.09 Sb _0.20 W _0.01 Ce _0.01 . The amount of silica supported was 47 mass% with respect to the total mass of the catalyst composed of the metal oxide and silica.

(Measurement of specific surface area)

As a result of measurement by the same method as in Example 1, the specific surface area was 10.2 m < 2 > / g.

(Removal of the stone body)

Was removed in the same manner as in Example 1.

(Total pore volume)

As a result of measurement by the same method as in Example 1, the total pore volume was 0.184 cm 3 / g.

(Pore distribution)

As a result of measurement by the same method as in Example 1, the ratio of the pore volume of the pores having a pore diameter of less than 60 nm was 9.6%, and the ratio of the pore volume of the pores having a pore diameter of 120 nm or more was 0.2%.

(Calculation of average pore diameter)

As a result of measurement by the same method as in Example 1, the average pore diameter was 72 nm.

(Measurement of crystallite size)

As a result of measurement by the same method as in Example 1, the crystallite size was 98 nm.

(Ammoxidation reaction of propane)

Using the oxide catalyst obtained above, propane was provided for the vapor-phase ammoxidation reaction by the following method. A mixed gas of propane: ammonia: oxygen: helium = 1: 1: 3: 18 in a molar ratio of propane: ammonia: oxygen: helium = 1 was prepared under a reaction pressure of 440 ° C at a reaction temperature of 440 ° C. Contact time 2.8 (sec · g / cc). After the reaction, the conversion of propane was 90.1%, the yield of acrylonitrile was 54.1%, and the combustion rate of ammonia was 19.6%.

(Example 17)

(Crude solution of niobium raw material liquid)

The liquid was adjusted in the same manner as in Example 1.

(Combination of raw material combination liquid in the combination tank)

To 100 kg of water were added 19.9 kg of ammonium heptamolybdate [(NH ₄ ) ₆ Mo ₇ O ₂₄ .4H ₂ O], 2.75 kg of ammonium metavanadate [NH ₄ VO ₃ ], 2,000 g of antimony trioxide [Sb ₂ O ₃ ] , 3.25 kg of cerium nitrate [Ce (NO ₃ ) ₃ .6H ₂ O] and 495 g of cerium nitrate [Ce (NO ₃ ) ₃ .6H ₂ O] were dissolved in 2 kg of water and heated at 95 ° C for 1 hour with stirring to obtain a raw material combination solution .

To 15.95 kg of the raw niobium solution was added 2.28 kg of hydrogen peroxide solution containing 30 mass% as H ₂ O ₂ . The liquid temperature was maintained at approximately 20 占 폚 and stirred and mixed to obtain a raw material combination solution (II).

Obtained after cooling the material combination solution (I) to 70 ℃, SiO ₂ average primary particle diameter with a sol having an average primary particle diameter of 23 nm containing a 30.2 wt% silica 31.0 kg, containing 30.0% by mass as SiO ₂ as a 6.80 kg of 13 nm silica sol was added. Then, 3.80 kg of hydrogen peroxide aqueous solution containing 30% by mass of H ₂ O ₂ was added and stirred at 55 ° C for 30 minutes. Then 516 g (50% purity) of the raw material combination solution (II) and the aqueous ammonium metatungstate solution were added, ). Further, 8.60 kg of powdered silica was dispersed in 77.4 kg of water and aged at 50 캜 for 1 hour as it was to obtain a raw material combination solution (III).

(Spray drying of the raw material combination liquid obtained in the combination tank)

Before the completion of the combination of the raw material combination liquid (III), hot air of 50 ° C adjusted to a feed rate of 80 kg / Hr and air heated to 210 ° C was supplied to the centrifugal spray dryer, Lt; / RTI >

The supply amount of the raw material combination liquid to be supplied to the spray dryer was adjusted so that the outlet temperature of the spray dryer was not changed, and the supply amount was 100 kg / Hr. In the meantime, the outlet temperature was 120 ± 5 ° C and there was no significant variation.

(Measurement of ultraviolet visible spectrum)

The obtained dried product was sampled every day, and 0.5 g of the obtained 10 sample products was measured by a diffuse reflection method in a range of 200 to 800 nm using JASCO UV / VIS Spectrometer V-650 manufactured by Nihon Bunko Co., Ltd. Spectralon manufactured by Labspere was used as a standard material for the baseline. The maximum absorbance was 1.02. The absorbance at 600 nm was 0.31 to 0.36, which was the absorbance with which high performance could be expected with reference to the description of JP-A-2009-148749. Therefore, the obtained spray dried product was used for classification operation without sorting.

(Classification operation)

The dried product thus obtained was classified using a sieve having a sieve size of 25 mu m to obtain a powder. The content of the particles of 25 mu m or less in the obtained powder was 0.8 mass% and the average particle diameter was 55 mu m.

(Firing of powder)

Seven slabs each having a height of 150 mm in a cylindrical sintered tube made of SUS having an inner diameter of 500 mm, a length of 3500 mm and a thickness of 20 mm were set so as to divide the length of the heating furnace into eight equal parts at a rate of 20 kg / hr And heated to 370 캜 for about 4 hours while rotating the fired tube at 4 rpm under a nitrogen gas flow of 600 N 터 l / min and heated to a heating furnace temperature of 370 캜 for 3 hours, And a shear fired product was obtained by shearing firing. Seven slabs each having a height of 150 mm in an SUS-made sintered pipe having an inner diameter of 500 mm, a length of 3500 mm and a thickness of 20 mm were installed so as to divide the length of the heating furnace into 8 equal parts. The sintering tube was rotated at 4 rpm , And shear debris was distributed at a rate of 15 kg / hr. At that time, with a hammering device provided with a hammer having a mass of 14 kg, which is made of stainless steel and the tip of the striking part was provided, the portion of the sintered tube on the powder introduction side (the portion not covered with the heating furnace) A temperature profile at which the temperature was raised to 550 ° C at a rate of 2 ° C / min under nitrogen gas flow of 500 N / min while being blown once at a rate of 5 ° C / The temperature of the furnace was adjusted so that the oxide catalyst was obtained.

(Composition of oxide catalyst)

As a result of analyzing the composition of the oxide catalyst, the composition of the metal oxide was MoV _0.21 Nb _0.09 Sb _0.20 W _0.01 Ce _0.01 . The amount of silica supported was 47 mass% with respect to the total mass of the catalyst composed of the metal oxide and silica.

(Measurement of specific surface area)

The specific surface area was found to be 17.4 m 2 / g as measured by the same method as in Example 1.

(Removal of the stone body)

Was removed in the same manner as in Example 1.

(Total pore volume)

As a result of measurement by the same method as in Example 1, the total pore volume was 0.270 cm 3 / g.

(Pore distribution)

As a result, it was found that the ratio of the pore volume of pores having a pore diameter of less than 60 nm was 31.2%, and the ratio of the pore volume of pores having a pore diameter of 120 nm or more was 0.1%.

(Calculation of average pore diameter)

As a result of measurement by the same method as in Example 1, the average pore diameter was 62 nm.

(Measurement of crystallite size)

As a result of measurement by the same method as in Example 1, the crystallite size was 44 nm.

(Ammoxidation reaction of propane)

Using the oxide catalyst obtained above, propane was provided for the vapor-phase ammoxidation reaction by the following method. A mixed gas of propane: ammonia: oxygen: helium = 1: 1: 3: 18 in a molar ratio of propane: ammonia: oxygen: helium = 1 was prepared under a reaction pressure of 440 ° C at a reaction temperature of 440 ° C. Contact time 2.8 (sec · g / cc). After the reaction, the conversion of propane was 90.1%, the yield of acrylonitrile was 53.8%, and the combustion rate of ammonia was 19.8%.

(Comparative Example 1)

(Crude solution of niobium raw material liquid)

The liquid was adjusted in the same manner as in Example 1.

(Combination of raw material combination liquid in the combination tank)

To 100 kg of water were added 21.0 kg of ammonium heptamolybdate [(NH ₄ ) ₆ Mo ₇ O ₂₄ .4H ₂ O], 2.91 kg of ammonium metavanadate [NH ₄ VO ₃ ], 2,000 g of antimony trioxide [Sb ₂ O ₃ ] Of cerium nitrate [Ce (NO ₃ ) ₃ .6H ₂ O] (524 g) dissolved in 2 kg of water was added and heated at 95 ° C for 1 hour while stirring to obtain a raw material combination solution (I) .

134 g of hydrogen peroxide solution containing 30 mass% as H ₂ O ₂ was added to 937 g of the niobium raw material liquid. The liquid temperature was maintained at approximately 20 占 폚 and stirred and mixed to obtain a raw material combination solution (II).

Obtained after cooling the material combination solution (I) to 70 ℃, SiO ₂ average primary particle diameter with a sol having an average primary particle diameter of 26 nm containing a 30.2 wt% silica 31.0 kg, containing 30.0% by mass as SiO ₂ as a 6.80 kg of 16 nm silica sol was added. Then, 4.02 kg of hydrogen peroxide aqueous solution containing 30% by mass of H ₂ O ₂ was added and stirred at 55 ° C for 30 minutes. Then 523 g (50% purity) of the raw material combination solution (II) and ammonium metatungstate solution were added, ). Further, 8.60 kg of powdered silica was dispersed in 77.4 kg of water and aged at 50 캜 for 1 hour as it was to obtain a raw material combination solution (III).

(Spray drying of the raw material combination liquid obtained in the combination tank)

Before the completion of the combination of the raw material combination liquid (III), hot air of 50 ° C adjusted to a feed rate of 80 kg / Hr and air heated to 210 ° C was supplied to the centrifugal spray dryer, Lt; / RTI >

The supply amount of the raw material combination liquid to be supplied to the spray dryer was adjusted so that the outlet temperature of the spray dryer was not changed, and the supply amount was 100 kg / Hr. In the meantime, the outlet temperature was 120 ± 5 ° C and there was no significant variation.

(Measurement of ultraviolet visible spectrum)

The obtained dried product was sampled every day, and 0.5 g of the obtained 10 sample products was measured by a diffuse reflection method in a range of 200 to 800 nm using JASCO UV / VIS Spectrometer V-650 manufactured by Nihon Bunko Co., Ltd. Spectralon manufactured by Labspere was used as a standard material for the baseline. The maximum absorbance was 1.02. The absorbance at 600 nm was 0.31 to 0.36, which was the absorbance with which high performance could be expected with reference to the description of JP-A-2009-148749. Therefore, the obtained spray dried product was used for classification operation without sorting.

(Classification operation)

The dried product thus obtained was classified using a sieve having a sieve size of 25 mu m to obtain a powder. The content of the particles of 25 mu m or less in the obtained powder was 0.8 mass% and the average particle diameter was 55 mu m.

(Firing of powder)

And fired in the same manner as in Example 2. [

(Composition of oxide catalyst)

As a result of analyzing the composition of the oxide catalyst, the composition of the metal oxide was MoV _0.21 Nb _0.005 Sb _0.20 W _0.01 Ce _0.01 . The amount of silica supported was 47 mass% with respect to the total mass of the catalyst composed of the metal oxide and silica.

(Measurement of specific surface area)

As a result of measurement by the same method as in Example 1, the specific surface area was 14.6 m 2 / g.

(Removal of the stone body)

Was removed in the same manner as in Example 1.

(Total pore volume)

As a result of measurement by the same method as in Example 1, the total pore volume was 0.329 cm 3 / g.

(Pore distribution)

The ratio of the pore volume of the pores having a pore diameter of less than 60 nm was 8.9%, and the ratio of the pore volume of the pores having a pore diameter of 120 nm or more was 0.4%.

(Calculation of average pore diameter)

As a result of measurement by the same method as in Example 1, the average pore diameter was 90 nm.

(Measurement of crystallite size)

As a result of measurement by the same method as in Example 1, the crystallite size was 120 nm.

(Ammoxidation reaction of propane)

Using the oxide catalyst obtained above, propane was provided for the vapor-phase ammoxidation reaction by the following method. A mixed gas of propane: ammonia: oxygen: helium = 1: 1: 3: 18 in a molar ratio of propane: ammonia: oxygen: helium = 1 was prepared under a reaction pressure of 440 ° C at a reaction temperature of 440 ° C. Contact time 2.8 (sec · g / cc). After the reaction, the conversion of propane was 87.5%, the yield of acrylonitrile was 51.5%, and the combustion rate of ammonia was 21.1%.

(Comparative Example 2)

(Crude solution of niobium raw material liquid)

The liquid was adjusted in the same manner as in Example 1.

(Combination of raw material combination liquid in the combination tank)

To 100 kg of water were added 19.9 kg of ammonium heptamolybdate [(NH ₄ ) ₆ Mo ₇ O ₂₄ .4H ₂ O], 2.75 kg of ammonium metavanadate [NH ₄ VO ₃ ], 2,000 g of antimony trioxide [Sb ₂ O ₃ ] , 3.25 kg of cerium nitrate [Ce (NO ₃ ) ₃ .6H ₂ O] and 495 g of cerium nitrate [Ce (NO ₃ ) ₃ .6H ₂ O] were dissolved in 2 kg of water and heated at 95 ° C for 1 hour with stirring to obtain a raw material combination solution .

To 15.95 kg of the raw niobium solution was added 2.28 kg of hydrogen peroxide solution containing 30 mass% as H ₂ O ₂ . The liquid temperature was maintained at approximately 20 占 폚 and stirred and mixed to obtain a raw material combination solution (II).

Obtained after cooling the material combination solution (I) to 70 ℃, SiO ₂ average primary particle diameter with a sol having an average primary particle diameter of 108 nm containing a 30.2 wt% silica 31.0 kg, containing 30.0% by mass as SiO ₂ as a 6.80 kg of 16 nm silica sol was added. Then, 3.80 kg of hydrogen peroxide aqueous solution containing 30% by mass of H ₂ O ₂ was added and stirred at 55 ° C for 30 minutes. Then 516 g (50% purity) of the raw material combination solution (II) and the aqueous ammonium metatungstate solution were added, ). Further, 8.60 kg of powdered silica was dispersed in 77.4 kg of water and aged at 50 캜 for 1 hour as it was to obtain a raw material combination solution (III).

(Spray drying of the raw material combination liquid obtained in the combination tank)

Before the completion of the combination of the raw material combination liquid (III), hot air of 50 ° C adjusted to a feed rate of 80 kg / Hr and air heated to 210 ° C was supplied to the centrifugal spray dryer, Lt; / RTI >

The supply amount of the raw material combination liquid to be supplied to the spray dryer was adjusted so that the outlet temperature of the spray dryer was not changed, and the supply amount was 100 kg / Hr. In the meantime, the outlet temperature was 120 ± 5 ° C and there was no significant variation.

(Measurement of ultraviolet visible spectrum)

The obtained dried product was sampled every day, and 0.5 g of the obtained 10 sample products was measured by a diffuse reflection method in a range of 200 to 800 nm using JASCO UV / VIS Spectrometer V-650 manufactured by Nihon Bunko Co., Ltd. Spectralon manufactured by Labspere was used as a standard material for the baseline. The maximum absorbance was 1.02. The absorbance at 600 nm was 0.31 to 0.36, which was the absorbance with which high performance could be expected with reference to the description of JP-A-2009-148749. Therefore, the obtained spray dried product was used for classification operation without sorting.

(Classification operation)

The dried product thus obtained was classified using a sieve having a sieve size of 25 mu m to obtain a powder. The content of the particles of 25 mu m or less in the obtained powder was 0.8 mass% and the average particle diameter was 55 mu m.

(Firing of powder)

And fired in the same manner as in Example 2. [

(Composition of oxide catalyst)

As a result of analyzing the composition of the oxide catalyst, the composition ratio of the metal oxide was MoV _0.21 Nb _0.09 Sb _0.20 W _0.01 Ce _0.01 . The amount of silica supported was 47 mass% with respect to the total mass of the catalyst composed of the metal oxide and silica.

(Measurement of specific surface area)

As a result of measurement by the same method as in Example 1, the specific surface area was 14.0 m 2 / g.

(Removal of the stone body)

Was removed in the same manner as in Example 1.

(Total pore volume)

As a result of measurement by the same method as in Example 1, the total pore volume was 0.543 cm 3 / g.

(Pore distribution)

As a result, the ratio of the pore volume of pores having a pore diameter of less than 60 nm was 1.3%, and the ratio of pore volume of pores having a pore diameter of 120 nm or more was 3.2%.

(Calculation of average pore diameter)

As a result of measurement by the same method as in Example 1, the average pore diameter was 155 nm.

(Measurement of crystallite size)

As a result of measurement by the same method as in Example 1, the crystallite size was 105 nm.

(Ammoxidation reaction of propane)

Using the oxide catalyst obtained above, propane was provided for the vapor-phase ammoxidation reaction by the following method. A mixed gas of propane: ammonia: oxygen: helium = 1: 1: 3: 18 in a molar ratio of propane: ammonia: oxygen: helium = 1 was prepared under a reaction pressure of 440 ° C at a reaction temperature of 440 ° C. Contact time 2.8 (sec · g / cc). After the reaction, the conversion of propane was 86.9%, the yield of acrylonitrile was 52.6%, and the combustion rate of ammonia was 19.3%.

(Comparative Example 3)

(Crude solution of niobium raw material liquid)

The liquid was adjusted in the same manner as in Example 1.

(Combination of raw material combination liquid in the combination tank)

To 100 kg of water were added 19.9 kg of ammonium heptamolybdate [(NH ₄ ) ₆ Mo ₇ O ₂₄ .4H ₂ O], 2.75 kg of ammonium metavanadate [NH ₄ VO ₃ ], 2,000 g of antimony trioxide [Sb ₂ O ₃ ] , 3.25 kg of cerium nitrate [Ce (NO ₃ ) ₃ .6H ₂ O] and 495 g of cerium nitrate [Ce (NO ₃ ) ₃ .6H ₂ O] were dissolved in 2 kg of water and heated at 95 ° C for 1 hour with stirring to obtain a raw material combination solution .

To 15.95 kg of the raw niobium solution was added 2.28 kg of hydrogen peroxide solution containing 30 mass% as H ₂ O ₂ . The liquid temperature was maintained at approximately 20 占 폚 and stirred and mixed to obtain a raw material combination solution (II).

The obtained raw material combination solution (I) After cooling to 70 ℃, SiO ₂ average primary particle diameter with a sol having an average primary particle diameter of 12 nm containing a 30.2 wt% silica 31.0 kg, containing 30.0% by mass as SiO ₂ as a 6.80 kg of 5 nm silica sol was added. Then, 3.80 kg of hydrogen peroxide aqueous solution containing 30% by mass of H ₂ O ₂ was added and stirred at 55 ° C for 30 minutes. Then 516 g (50% purity) of the raw material combination solution (II) and the aqueous ammonium metatungstate solution were added, ). Further, 8.60 kg of powdered silica was dispersed in 77.4 kg of water and aged at 50 캜 for 1 hour as it was to obtain a raw material combination solution (III).

(Spray drying of the raw material combination liquid obtained in the combination tank)

Before the completion of the combination of the raw material combination liquid (III), hot air of 50 ° C adjusted to a feed rate of 80 kg / Hr and air heated to 210 ° C was supplied to the centrifugal spray dryer, Lt; / RTI >

The supply amount of the raw material combination liquid to be supplied to the spray dryer was adjusted so that the outlet temperature of the spray dryer was not changed, and the supply amount was 100 kg / Hr. In the meantime, the outlet temperature was 120 ± 5 ° C and there was no significant variation.

(Measurement of ultraviolet visible spectrum)

The obtained dried product was sampled every day, and 0.5 g of the obtained 10 sample products was measured by a diffuse reflection method in a range of 200 to 800 nm using JASCO UV / VIS Spectrometer V-650 manufactured by Nihon Bunko Co., Ltd. Spectralon manufactured by Labspere was used as a standard material for the baseline. The maximum absorbance was 1.02. The absorbance at 600 nm was 0.31 to 0.36, which was the absorbance with which high performance could be expected with reference to the description of JP-A-2009-148749. Therefore, the obtained spray dried product was used for classification operation without sorting.

(Classification operation)

The dried product thus obtained was classified using a sieve having a sieve size of 25 mu m to obtain a powder. The content of the particles of 25 mu m or less in the obtained powder was 0.8 mass% and the average particle diameter was 55 mu m.

(Firing of powder)

And fired in the same manner as in Example 2. [

(Composition of oxide catalyst)

As a result of analyzing the composition of the oxide catalyst, the composition of the metal oxide was MoV _0.21 Nb _0.09 Sb _0.20 W _0.01 Ce _0.01 . The amount of silica supported was 47 mass% with respect to the total mass of the catalyst composed of the metal oxide and silica.

(Measurement of specific surface area)

As a result of measurement by the same method as in Example 1, the specific surface area was 13.8 m 2 / g.

(Removal of the stone body)

Was removed in the same manner as in Example 1.

(Total pore volume)

As a result of measurement by the same method as in Example 1, the total pore volume was 0.086 cm 3 / g.

(Pore distribution)

The ratio of the pore volume of the pores having a pore diameter of less than 60 nm was 88.2%, and the ratio of the pore volume of the pores having a pore diameter of 120 nm or more was 0%.

(Calculation of average pore diameter)

As a result of measurement by the same method as in Example 1, the average pore diameter was 25 nm.

(Measurement of crystallite size)

As a result of measurement by the same method as in Example 1, the crystallite size was 104 nm.

(Ammoxidation reaction of propane)

Using the oxide catalyst obtained above, propane was provided for the vapor-phase ammoxidation reaction by the following method. A mixed gas of propane: ammonia: oxygen: helium = 1: 1: 3: 18 in a molar ratio of propane: ammonia: oxygen: helium = 1 was prepared under a reaction pressure of 440 ° C at a reaction temperature of 440 ° C. Contact time 2.8 (sec · g / cc). After the reaction, the conversion of propane was 87.1%, the yield of acrylonitrile was 53.1%, and the combustion rate of ammonia was 22.6%.

(Comparative Example 4)

(Crude solution of niobium raw material liquid)

The liquid was adjusted in the same manner as in Example 1.

(Combination of raw material combination liquid in the combination tank)

To 100 kg of water were added 19.9 kg of ammonium heptamolybdate [(NH ₄ ) ₆ Mo ₇ O ₂₄ .4H ₂ O], 2.75 kg of ammonium metavanadate [NH ₄ VO ₃ ], 2,000 g of antimony trioxide [Sb ₂ O ₃ ] , 3.25 kg of cerium nitrate [Ce (NO ₃ ) ₃ .6H ₂ O] and 495 g of cerium nitrate [Ce (NO ₃ ) ₃ .6H ₂ O] were dissolved in 2 kg of water and heated at 95 ° C for 1 hour with stirring to obtain a raw material combination solution .

To 15.95 kg of the raw niobium solution was added 2.28 kg of hydrogen peroxide solution containing 30 mass% as H ₂ O ₂ . The liquid temperature was maintained at approximately 20 占 폚 and stirred and mixed to obtain a raw material combination solution (II).

After the obtained raw material combination solution (I) was cooled to 70 캜, 31.0 kg of silica sol containing 30.2% by mass of SiO ₂ and having an average primary particle diameter of 110 nm and 30.0% by mass of SiO ₂ and having an average primary particle diameter 6.80 kg of 16 nm silica sol was added. Then, 3.80 kg of hydrogen peroxide aqueous solution containing 30% by mass of H ₂ O ₂ was added and stirred at 55 ° C for 30 minutes. Then 516 g (50% purity) of the raw material combination solution (II) and the aqueous ammonium metatungstate solution were added, ). Further, 8.60 kg of powdered silica was dispersed in 77.4 kg of water and aged at 50 캜 for 1 hour as it was to obtain a raw material combination solution (III).

(Spray drying of the raw material combination liquid obtained in the combination tank)

Before the completion of the combination of the raw material combination liquid (III), hot air of 50 ° C adjusted to a feed rate of 80 kg / Hr and air heated to 210 ° C was supplied to the centrifugal spray dryer, Lt; / RTI >

The supply amount of the raw material combination liquid to be supplied to the spray dryer was adjusted so that the outlet temperature of the spray dryer was not changed, and the supply amount was 100 kg / Hr. In the meantime, the outlet temperature was 120 ± 5 ° C and there was no significant variation.

(Measurement of ultraviolet visible spectrum)

The obtained dried product was sampled every day, and 0.5 g of the obtained 10 sample products was measured by a diffuse reflection method in a range of 200 to 800 nm using JASCO UV / VIS Spectrometer V-650 manufactured by Nihon Bunko Co., Ltd. Spectralon manufactured by Labspere was used as a standard material for the baseline. The maximum absorbance was 1.02. The absorbance at 600 nm was 0.31 to 0.36, which was the absorbance with which high performance could be expected with reference to the description of JP-A-2009-148749. Therefore, the obtained spray dried product was used for classification operation without sorting.

(Classification operation)

The dried product thus obtained was classified using a sieve having a sieve size of 25 mu m to obtain a powder. The content of the particles of 25 mu m or less in the obtained powder was 0.8 mass% and the average particle diameter was 55 mu m.

(Firing of powder)

Seven slabs each having a height of 150 mm in a cylindrical sintered tube made of SUS having an inner diameter of 500 mm, a length of 3500 mm and a thickness of 20 mm were set so as to divide the length of the heating furnace into eight equal parts at a rate of 20 kg / hr And heated to 370 캜 for about 4 hours while rotating the fired tube at 4 rpm under a nitrogen gas flow of 600 N 터 l / min and heated to a heating furnace temperature of 370 캜 for 3 hours, And a shear fired product was obtained by shearing firing. Seven slabs each having a height of 150 mm in an SUS-made sintered pipe having an inner diameter of 500 mm, a length of 3500 mm and a thickness of 20 mm were installed so as to divide the length of the heating furnace into 8 equal parts. The sintering tube was rotated at 4 rpm , And shear debris was distributed at a rate of 15 kg / hr. At that time, with a hammering device provided with a hammer having a mass of 14 kg, which is made of stainless steel and the tip of the striking part was provided, the portion of the sintered tube on the powder introduction side (the portion not covered with the heating furnace) The temperature profile of raising the temperature to 695 캜 at a rate of 2 캜 / min under a nitrogen gas flow of 500 N / min while bombarding the substrate at a rate of 0.5 캜 / min while heating the substrate at 695 캜 for 4 hours, The temperature of the furnace was adjusted so that the oxide catalyst was obtained.

(Composition of oxide catalyst)

As a result of analyzing the composition of the oxide catalyst, the composition ratio of the metal oxide was MoV _0.21 Nb _0.09 Sb _0.20 W _0.01 Ce _0.01 . The amount of silica supported was 47 mass% with respect to the total mass of the catalyst composed of the metal oxide and silica.

(Measurement of specific surface area)

As a result of measurement by the same method as in Example 1, the specific surface area was 8.1 m 2 / g.

(Removal of the stone body)

Was removed in the same manner as in Example 1.

(Total pore volume)

As a result of measurement by the same method as in Example 1, the total pore volume was 0.324 cm 3 / g.

(Pore distribution)

As a result of measurement by the same method as in Example 1, the ratio of the pore volume of the pores having a pore diameter of less than 60 nm was 1.1%, and the ratio of the pore volume of the pores having a pore diameter of 120 nm or more was 3.8%.

(Calculation of average pore diameter)

As a result of measurement by the same method as in Example 1, the average pore diameter was 160 nm.

(Measurement of crystallite size)

As a result of measurement by the same method as in Example 1, the crystallite size was 390 nm.

(Ammoxidation reaction of propane)

Using the oxide catalyst obtained above, propane was provided for the vapor-phase ammoxidation reaction by the following method. A mixed gas of propane: ammonia: oxygen: helium = 1: 1: 3: 18 in a molar ratio of propane: ammonia: oxygen: helium = 1 was prepared under a reaction pressure of 440 ° C at a reaction temperature of 440 ° C. Contact time 2.8 (sec · g / cc). After the reaction, the conversion of propane was 85.9%, the yield of acrylonitrile was 52.2%, and the combustion rate of ammonia was 20.1%.

(Comparative Example 5)

(Crude solution of niobium raw material liquid)

The liquid was adjusted in the same manner as in Example 1.

(Combination of raw material combination liquid in the combination tank)

To 100 kg of water were added 19.9 kg of ammonium heptamolybdate [(NH ₄ ) ₆ Mo ₇ O ₂₄ .4H ₂ O], 2.75 kg of ammonium metavanadate [NH ₄ VO ₃ ], 2,000 g of antimony trioxide [Sb ₂ O ₃ ] , 3.25 kg of cerium nitrate [Ce (NO ₃ ) ₃ .6H ₂ O] and 495 g of cerium nitrate [Ce (NO ₃ ) ₃ .6H ₂ O] were dissolved in 2 kg of water and heated at 95 ° C for 1 hour with stirring to obtain a raw material combination solution .

To 15.95 kg of the raw niobium solution was added 2.28 kg of hydrogen peroxide solution containing 30 mass% as H ₂ O ₂ . The liquid temperature was maintained at approximately 20 占 폚 and stirred and mixed to obtain a raw material combination solution (II).

Obtained after cooling the material combination solution (I) to 70 ℃, SiO ₂ average primary particle diameter with a sol having an average primary particle diameter of 108 nm containing a 30.2 wt% silica 31.0 kg, containing 30.0% by mass as SiO ₂ as a 6.80 kg of 16 nm silica sol was added. Then, 3.80 kg of hydrogen peroxide aqueous solution containing 30% by mass of H ₂ O ₂ was added and stirred at 55 ° C for 30 minutes. Then 516 g (50% purity) of the raw material combination solution (II) and the aqueous ammonium metatungstate solution were added, ). Further, 8.60 kg of powdered silica was dispersed in 77.4 kg of water and aged at 50 캜 for 1 hour as it was to obtain a raw material combination solution (III).

(Spray drying of the raw material combination liquid obtained in the combination tank)

Before the completion of the combination of the raw material combination liquid (III), hot air of 50 ° C adjusted to a feed rate of 80 kg / Hr and air heated to 210 ° C was supplied to the centrifugal spray dryer, Lt; / RTI >

The supply amount of the raw material combination liquid to be supplied to the spray dryer was adjusted so that the outlet temperature of the spray dryer was not changed, and the supply amount was 100 kg / Hr. In the meantime, the outlet temperature was 120 ± 5 ° C and there was no significant variation.

(Measurement of ultraviolet visible spectrum)

The obtained dried product was sampled every day, and 0.5 g of the obtained 10 sample products was measured by a diffuse reflection method in a range of 200 to 800 nm using JASCO UV / VIS Spectrometer V-650 manufactured by Nihon Bunko Co., Ltd. Spectralon manufactured by Labspere was used as a standard material for the baseline. The maximum absorbance was 1.02. The absorbance at 600 nm was 0.31 to 0.36, which was the absorbance with which high performance could be expected with reference to the description of JP-A-2009-148749. Therefore, the obtained spray dried product was used for classification operation without sorting.

(Classification operation)

The dried product thus obtained was classified using a sieve having a sieve size of 25 mu m to obtain a powder. The content of the particles of 25 mu m or less in the obtained powder was 0.8 mass% and the average particle diameter was 55 mu m.

(Firing of powder)

Seven slabs each having a height of 150 mm in a cylindrical sintered tube made of SUS having an inner diameter of 500 mm, a length of 3500 mm and a thickness of 20 mm were set so as to divide the length of the heating furnace into eight equal parts at a rate of 20 kg / hr And heated to 370 캜 for about 4 hours while rotating the fired tube at 4 rpm under a nitrogen gas flow of 600 N 터 l / min and heated to a heating furnace temperature of 370 캜 for 3 hours, And a shear fired product was obtained by shearing firing. Seven slabs each having a height of 150 mm in an SUS-made sintered pipe having an inner diameter of 500 mm, a length of 3500 mm and a thickness of 20 mm were installed so as to divide the length of the heating furnace into 8 equal parts. The sintering tube was rotated at 4 rpm , And shear debris was distributed at a rate of 15 kg / hr. At that time, with a hammering device provided with a hammer having a mass of 14 kg, which is made of stainless steel and the tip of the striking part was provided, the portion of the sintered tube on the powder introduction side (the portion not covered with the heating furnace) The temperature profile was raised to 670 캜 at a rate of 2 캜 / min under a nitrogen gas flow of 500 N / min while being blown once at a rate of 5 캜 for 5 seconds, followed by firing at 670 캜 for 1 hour, The temperature of the furnace was adjusted so that the oxide catalyst was obtained.

(Composition of oxide catalyst)

As a result of analyzing the composition of the oxide catalyst, the composition ratio of the metal oxide was MoV _0.21 Nb _0.09 Sb _0.20 W _0.01 Ce _0.01 . The amount of silica supported was 47 mass% with respect to the total mass of the catalyst composed of the metal oxide and silica.

(Measurement of specific surface area)

As a result of measurement by the same method as in Example 1, the specific surface area was found to be 16.2 m < 2 > / g.

(Removal of the stone body)

Was removed in the same manner as in Example 1.

(Total pore volume)

As a result of measurement by the same method as in Example 1, the total pore volume was 0.559 cm 3 / g.

(Pore distribution)

As a result of measurement by the same method as in Example 1, the ratio of the pore volume of the pores having a pore diameter of less than 60 nm was 2.3%, and the ratio of the pore volume of the pores having a pore diameter of 120 nm or more was 3.2%.

(Calculation of average pore diameter)

As a result of measurement by the same method as in Example 1, the average pore diameter was 138 nm.

(Measurement of crystallite size)

As a result of measurement by the same method as in Example 1, the crystallite size was 20 nm.

(Ammoxidation reaction of propane)

Using the oxide catalyst obtained above, propane was provided for the vapor-phase ammoxidation reaction by the following method. A mixed gas of propane: ammonia: oxygen: helium = 1: 1: 3: 18 in a molar ratio of propane: ammonia: oxygen: helium = 1 was prepared under a reaction pressure of 440 ° C at a reaction temperature of 440 ° C. Contact time 2.8 (sec · g / cc). After the reaction, the conversion of propane was 86.5%, the yield of acrylonitrile was 52.1%, and the combustion rate of ammonia was 19.3%.

(Comparative Example 6)

(Crude solution of niobium raw material liquid)

The liquid was adjusted in the same manner as in Example 1.

(Combination of raw material combination liquid in the combination tank)

To 100 kg of water were added 19.9 kg of ammonium heptamolybdate [(NH ₄ ) ₆ Mo ₇ O ₂₄ .4H ₂ O], 2.75 kg of ammonium metavanadate [NH ₄ VO ₃ ], 2,000 g of antimony trioxide [Sb ₂ O ₃ ] , 3.25 kg of cerium nitrate [Ce (NO ₃ ) ₃ .6H ₂ O] and 495 g of cerium nitrate [Ce (NO ₃ ) ₃ .6H ₂ O] were dissolved in 2 kg of water and heated at 95 ° C for 1 hour with stirring to obtain a raw material combination solution .

To 15.95 kg of the raw niobium solution was added 2.28 kg of hydrogen peroxide solution containing 30 mass% as H ₂ O ₂ . The liquid temperature was maintained at approximately 20 占 폚 and stirred and mixed to obtain a raw material combination solution (II).

The obtained raw material combination solution (I) After cooling to 70 ℃, SiO ₂ average primary particle diameter with a sol having an average primary particle diameter of 12 nm containing a 30.2 wt% silica 31.0 kg, containing 30.0% by mass as SiO ₂ as a 6.80 kg of 8 nm silica sol was added. Then, 3.80 kg of hydrogen peroxide aqueous solution containing 30% by mass of H ₂ O ₂ was added and stirred at 55 ° C for 30 minutes. Then 516 g (50% purity) of the raw material combination solution (II) and the aqueous ammonium metatungstate solution were added, ). Further, 8.60 kg of powdered silica was dispersed in 77.4 kg of water and aged at 50 캜 for 1 hour as it was to obtain a raw material combination solution (III).

(Spray drying of the raw material combination liquid obtained in the combination tank)

Before the completion of the combination of the raw material combination liquid (III), hot air of 50 ° C adjusted to a feed rate of 80 kg / Hr and air heated to 210 ° C was supplied to the centrifugal spray dryer, Lt; / RTI >

The supply amount of the raw material combination liquid to be supplied to the spray dryer was adjusted so that the outlet temperature of the spray dryer was not changed, and the supply amount was 100 kg / Hr. In the meantime, the outlet temperature was 120 ± 5 ° C and there was no significant variation.

(Measurement of ultraviolet visible spectrum)

The obtained dried product was sampled every day, and 0.5 g of the obtained 10 sample products was measured by a diffuse reflection method in a range of 200 to 800 nm using JASCO UV / VIS Spectrometer V-650 manufactured by Nihon Bunko Co., Ltd. Spectralon manufactured by Labspere was used as a standard material for the baseline. The maximum absorbance was 1.02. The absorbance at 600 nm was 0.31 to 0.36, which was the absorbance with which high performance could be expected with reference to the description of JP-A-2009-148749. Therefore, the obtained spray dried product was used for classification operation without sorting.

(Classification operation)

The dried product thus obtained was classified using a sieve having a sieve size of 25 mu m to obtain a powder. The content of the particles of 25 mu m or less in the obtained powder was 0.8 mass% and the average particle diameter was 55 mu m.

(Firing of powder)

Seven slabs each having a height of 150 mm in a cylindrical sintered tube made of SUS having an inner diameter of 500 mm, a length of 3500 mm and a thickness of 20 mm were set so as to divide the length of the heating furnace into eight equal parts at a rate of 20 kg / hr And heated to 370 캜 for about 4 hours while rotating the fired tube at 4 rpm under a nitrogen gas flow of 600 N 터 l / min and heated to a heating furnace temperature of 370 캜 for 3 hours, And a shear fired product was obtained by shearing firing. Seven slabs each having a height of 150 mm in an SUS-made sintered pipe having an inner diameter of 500 mm, a length of 3500 mm and a thickness of 20 mm were installed so as to divide the length of the heating furnace into 8 equal parts. The sintering tube was rotated at 4 rpm , And shear debris was distributed at a rate of 15 kg / hr. At that time, with a hammering device provided with a hammer having a mass of 14 kg, which is made of stainless steel and the tip of the striking part was provided, was placed in the powder introduction side portion (the portion not covered with the heating furnace) A temperature profile at which the temperature was raised to 695 캜 at a rate of 2 캜 / min under a nitrogen gas flow of 500 N / min while being blown once at a rate of 5 캜 for 5 seconds, and then fired at 695 캜 for 4 hours, The temperature of the furnace was adjusted so that the oxide catalyst was obtained.

(Composition of oxide catalyst)

As a result of analyzing the composition of the oxide catalyst, the composition ratio of the metal oxide was MoV _0.21 Nb _0.09 Sb _0.20 W _0.01 Ce _0.01 . The amount of silica supported was 47 mass% with respect to the total mass of the catalyst composed of the metal oxide and silica.

(Measurement of specific surface area)

As a result of measurement by the same method as in Example 1, the specific surface area was 9.2 m < 2 > / g.

(Removal of the stone body)

Was removed in the same manner as in Example 1.

(Total pore volume)

As a result of measurement by the same method as in Example 1, the total pore volume was 0.097 cm 3 / g.

(Pore distribution)

The ratio of the pore volume of pores having a pore diameter of less than 60 nm was 68.4%, and the ratio of pore volume of pores having a pore diameter of 120 nm or more was 0%.

(Calculation of average pore diameter)

As a result of measurement by the same method as in Example 1, the average pore diameter was 42 nm.

(Measurement of crystallite size)

As a result of measurement by the same method as in Example 1, the crystallite size was 375 nm.

(Ammoxidation reaction of propane)

Using the oxide catalyst obtained above, propane was provided for the vapor-phase ammoxidation reaction by the following method. A mixed gas of propane: ammonia: oxygen: helium = 1: 1: 3: 18 in a molar ratio of propane: ammonia: oxygen: helium = 1 was prepared under a reaction pressure of 440 ° C at a reaction temperature of 440 ° C. Contact time 2.8 (sec · g / cc). After the reaction, the conversion of propane was 87.0%, the yield of acrylonitrile was 52.3%, and the combustion rate of ammonia was 23.1%.

(Comparative Example 7)

(Crude solution of niobium raw material liquid)

The liquid was adjusted in the same manner as in Example 1.

(Combination of raw material combination liquid in the combination tank)

To 100 kg of water were added 19.9 kg of ammonium heptamolybdate [(NH ₄ ) ₆ Mo ₇ O ₂₄ .4H ₂ O], 2.75 kg of ammonium metavanadate [NH ₄ VO ₃ ], 2,000 g of antimony trioxide [Sb ₂ O ₃ ] , 3.25 kg of cerium nitrate [Ce (NO ₃ ) ₃ .6H ₂ O] and 495 g of cerium nitrate [Ce (NO ₃ ) ₃ .6H ₂ O] were dissolved in 2 kg of water and heated at 95 ° C for 1 hour with stirring to obtain a raw material combination solution .

To 15.95 kg of the raw niobium solution was added 2.28 kg of hydrogen peroxide solution containing 30 mass% as H ₂ O ₂ . The liquid temperature was maintained at approximately 20 占 폚 and stirred and mixed to obtain a raw material combination solution (II).

After the obtained raw material combination solution (I) was cooled to 70 캜, 31.0 kg of silica sol containing 30.2% by mass of SiO ₂ and having an average primary particle diameter of 10 nm and 30.0% by mass of SiO ₂ containing an average primary particle diameter 6.80 kg of 13 nm silica sol was added. Then, 3.80 kg of hydrogen peroxide aqueous solution containing 30% by mass of H ₂ O ₂ was added and stirred at 55 ° C for 30 minutes. Then 516 g (50% purity) of the raw material combination solution (II) and the aqueous ammonium metatungstate solution were added, ). Further, 8.60 kg of powdered silica was dispersed in 77.4 kg of water and aged at 50 캜 for 1 hour as it was to obtain a raw material combination solution (III).

(Spray drying of the raw material combination liquid obtained in the combination tank)

Before the completion of the combination of the raw material combination liquid (III), hot air of 50 ° C adjusted to a feed rate of 80 kg / Hr and air heated to 210 ° C was supplied to the centrifugal spray dryer, Lt; / RTI >

The supply amount of the raw material combination liquid to be supplied to the spray dryer was adjusted so that the outlet temperature of the spray dryer was not changed, and the supply amount was 100 kg / Hr. In the meantime, the outlet temperature was 120 ± 5 ° C and there was no significant variation.

(Measurement of ultraviolet visible spectrum)

The obtained dried product was sampled every day, and 0.5 g of the obtained 10 sample products was measured by a diffuse reflection method in a range of 200 to 800 nm using JASCO UV / VIS Spectrometer V-650 manufactured by Nihon Bunko Co., Ltd. Spectralon manufactured by Labspere was used as a standard material for the baseline. The maximum absorbance was 1.02. The absorbance at 600 nm was 0.31 to 0.36, which was the absorbance with which high performance could be expected with reference to the description of JP-A-2009-148749. Therefore, the obtained spray dried product was used for classification operation without sorting.

(Classification operation)

The dried product thus obtained was classified using a sieve having a sieve size of 25 mu m to obtain a powder. The content of the particles of 25 mu m or less in the obtained powder was 0.8 mass% and the average particle diameter was 55 mu m.

(Firing of powder)

Seven slabs each having a height of 150 mm in a cylindrical sintered tube made of SUS having an inner diameter of 500 mm, a length of 3500 mm and a thickness of 20 mm were set so as to divide the length of the heating furnace into eight equal parts at a rate of 20 kg / hr And heated to 370 캜 for about 4 hours while rotating the fired tube at 4 rpm under a nitrogen gas flow of 600 N 터 l / min and heated to a heating furnace temperature of 370 캜 for 3 hours, And a shear fired product was obtained by shearing firing. Seven slabs each having a height of 150 mm in an SUS-made sintered pipe having an inner diameter of 500 mm, a length of 3500 mm and a thickness of 20 mm were installed so as to divide the length of the heating furnace into 8 equal parts. The sintering tube was rotated at 4 rpm , And shear debris was distributed at a rate of 15 kg / hr. At that time, with a hammering device provided with a hammer having a mass of 14 kg, which is made of stainless steel and the tip of the striking part was provided, was placed in the powder introduction side portion (the portion not covered with the heating furnace) A temperature profile at which the temperature was raised to 670 캜 at a rate of 2 캜 / min under a nitrogen gas flow of 500 N / min while being blown once at a rate of 5 캜 for 5 seconds and then fired at 670 캜 for 1 hour, The temperature of the furnace was adjusted so that the oxide catalyst was obtained.

(Composition of oxide catalyst)

As a result of analyzing the composition of the oxide catalyst, the composition ratio of the metal oxide was MoV _0.21 Nb _0.09 Sb _0.20 W _0.01 Ce _0.01 . The amount of silica supported was 47 mass% with respect to the total mass of the catalyst composed of the metal oxide and silica.

(Measurement of specific surface area)

As a result of measurement by the same method as in Example 1, the specific surface area was found to be 20.3 m < 2 > / g.

(Removal of the stone body)

Was removed in the same manner as in Example 1.

(Total pore volume)

As a result of measurement by the same method as in Example 1, the total pore volume was 0.112 cm 3 / g.

(Pore distribution)

The ratio of the pore volume of the pores having a pore diameter of less than 60 nm was 91.4%, and the ratio of the pore volume of the pores having a pore diameter of 120 nm or more was 0%.

(Calculation of average pore diameter)

As a result of measurement by the same method as in Example 1, the average pore diameter was 22 nm.

(Measurement of crystallite size)

As a result of measurement by the same method as in Example 1, the crystallite size was 24 nm.

(Ammoxidation reaction of propane)

Using the oxide catalyst obtained above, propane was provided for the vapor-phase ammoxidation reaction by the following method. A mixed gas of propane: ammonia: oxygen: helium = 1: 1: 3: 18 in a molar ratio of propane: ammonia: oxygen: helium = 1 was prepared under a reaction pressure of 440 ° C at a reaction temperature of 440 ° C. Contact time 2.8 (sec · g / cc). After the reaction, the conversion of propane was 86.30%, the yield of acrylonitrile was 52.1%, and the combustion rate of ammonia was 21.1%.

(Comparative Example 8)

(Crude solution of niobium raw material liquid)

The liquid was adjusted in the same manner as in Example 1.

(Combination of raw material combination liquid in the combination tank)

To 100 kg of water were added 19.9 kg of ammonium heptamolybdate [(NH ₄ ) ₆ Mo ₇ O ₂₄ .4H ₂ O], 2.75 kg of ammonium metavanadate [NH ₄ VO ₃ ], 2,000 g of antimony trioxide [Sb ₂ O ₃ ] , 3.25 kg of cerium nitrate [Ce (NO ₃ ) ₃ .6H ₂ O] and 495 g of cerium nitrate [Ce (NO ₃ ) ₃ .6H ₂ O] were dissolved in 2 kg of water and heated at 95 ° C for 1 hour with stirring to obtain a raw material combination solution .

To 15.95 kg of the raw niobium solution was added 2.28 kg of hydrogen peroxide solution containing 30 mass% as H ₂ O ₂ . The liquid temperature was maintained at approximately 20 占 폚 and stirred and mixed to obtain a raw material combination solution (II).

After the obtained raw material combination solution (I) was cooled to 70 캜, 31.0 kg of silica sol containing 30.2% by mass of SiO ₂ and having an average primary particle diameter of 15 nm and 30.0% by mass of SiO ₂ containing an average primary particle diameter 6.80 kg of 5 nm silica sol was added. Subsequently, 3.80 g of hydrogen peroxide aqueous solution containing 30 mass% as H ₂ O ₂ was added and stirred at 55 ° C for 30 minutes. Then 516 g (50% purity) of the raw material combination solution (II) and the aqueous ammonium metatungstate solution were added, ). Further, 8.60 kg of powdered silica was dispersed in 77.4 kg of water and aged at 50 캜 for 1 hour as it was to obtain a raw material combination solution (III).

(Spray drying of the raw material combination liquid obtained in the combination tank)

Before the completion of the combination of the raw material combination liquid (III), hot air of 50 ° C adjusted to a feed rate of 80 kg / Hr and air heated to 210 ° C was supplied to the centrifugal spray dryer, Lt; / RTI >

The supply amount of the raw material combination liquid to be supplied to the spray dryer was adjusted so that the outlet temperature of the spray dryer was not changed, and the supply amount was 100 kg / Hr. In the meantime, the outlet temperature was 120 ± 5 ° C and there was no significant variation.

(Measurement of ultraviolet visible spectrum)

The obtained dried product was sampled every day, and 0.5 g of the obtained 10 sample products was measured by a diffuse reflection method in a range of 200 to 800 nm using JASCO UV / VIS Spectrometer V-650 manufactured by Nihon Bunko Co., Ltd. Spectralon manufactured by Labspere was used as a standard material for the baseline. The maximum absorbance was 1.02. The absorbance at 600 nm was 0.31 to 0.36, which was the absorbance with which high performance could be expected with reference to the description of JP-A-2009-148749. Therefore, the obtained spray dried product was used for classification operation without sorting.

(Classification operation)

The dried product thus obtained was classified using a sieve having a sieve size of 25 mu m to obtain a powder. The content of the particles of 25 mu m or less in the obtained powder was 0.8 mass% and the average particle diameter was 55 mu m.

(Firing of powder)

Seven slabs each having a height of 150 mm in a cylindrical sintered tube made of SUS having an inner diameter of 500 mm, a length of 3500 mm and a thickness of 20 mm were set so as to divide the length of the heating furnace into eight equal parts at a rate of 20 kg / hr And heated to 370 캜 for about 4 hours while rotating the fired tube at 4 rpm under a nitrogen gas flow of 600 N 터 l / min and heated to a heating furnace temperature of 370 캜 for 3 hours, And a shear fired product was obtained by shearing firing. Seven slabs each having a height of 150 mm in an SUS-made sintered pipe having an inner diameter of 500 mm, a length of 3500 mm and a thickness of 20 mm were installed so as to divide the length of the heating furnace into 8 equal parts. The sintering tube was rotated at 4 rpm , And shear debris was distributed at a rate of 15 kg / hr. At that time, with a hammering device provided with a hammer having a mass of 14 kg, which is made of stainless steel and the tip of the striking part was provided, was placed in the powder introduction side portion (the portion not covered with the heating furnace) A temperature profile at a rate of 2 DEG C / min to 700 DEG C under nitrogen gas flow of 500 N / min while heating at 700 DEG C for 2 hours while blowing once at a rate of 5 DEG C / The temperature of the furnace was adjusted so that the oxide catalyst was obtained.

(Composition of oxide catalyst)

As a result of analyzing the composition of the oxide catalyst, the composition ratio of the metal oxide was MoV _0.21 Nb _0.09 Sb _0.20 W _0.01 Ce _0.01 . The amount of silica supported was 47 mass% with respect to the total mass of the catalyst composed of the metal oxide and silica.

(Measurement of specific surface area)

As a result of measurement by the same method as in Example 1, the specific surface area was 4.2 m 2 / g.

(Removal of the stone body)

Was removed in the same manner as in Example 1.

(Total pore volume)

As a result of measurement by the same method as in Example 1, the total pore volume was 0.055 cm 3 / g.

(Pore distribution)

As a result of measurement by the same method as in Example 1, the ratio of the pore volume of the pores having a pore diameter of less than 60 nm was 54.6%, and the ratio of the pore volume of the pores having a pore diameter of 120 nm or more was 0%.

(Calculation of average pore diameter)

As a result of measurement by the same method as in Example 1, the average pore diameter was 52 nm.

(Measurement of crystallite size)

As a result of measurement by the same method as in Example 1, the crystallite size was 204 nm.

(Ammoxidation reaction of propane)

Using the oxide catalyst obtained above, propane was provided for the vapor-phase ammoxidation reaction by the following method. A mixed gas of propane: ammonia: oxygen: helium = 1: 1: 3: 18 in a molar ratio of propane: ammonia: oxygen: helium = 1 was prepared under a reaction pressure of 440 ° C at a reaction temperature of 440 ° C. Contact time 2.8 (sec · g / cc). After the reaction, the conversion of propane was 86.2%, the yield of acrylonitrile was 50.6%, and the combustion rate of ammonia was 22.8%.

(Comparative Example 9)

(Crude solution of niobium raw material liquid)

The liquid was adjusted in the same manner as in Example 1.

(Combination of raw material combination liquid in the combination tank)

To 100 kg of water were added 19.9 kg of ammonium heptamolybdate [(NH ₄ ) ₆ Mo ₇ O ₂₄ .4H ₂ O], 2.75 kg of ammonium metavanadate [NH ₄ VO ₃ ], 2,000 g of antimony trioxide [Sb ₂ O ₃ ] , 3.25 kg of cerium nitrate [Ce (NO ₃ ) ₃ .6H ₂ O] and 495 g of cerium nitrate [Ce (NO ₃ ) ₃ .6H ₂ O] were dissolved in 2 kg of water and heated at 95 ° C for 1 hour with stirring to obtain a raw material combination solution .

To 15.95 kg of the raw niobium solution was added 2.28 kg of hydrogen peroxide solution containing 30 mass% as H ₂ O ₂ . The liquid temperature was maintained at approximately 20 占 폚 and stirred and mixed to obtain a raw material combination solution (II).

After the obtained raw material combination solution (I) was cooled to 70 캜, 34.7 kg of silica sol having an average primary particle diameter of 23 nm containing 30.2% by mass as SiO ₂ was added. Then, 3.80 kg of hydrogen peroxide aqueous solution containing 30% by mass of H ₂ O ₂ was added and stirred at 55 ° C for 30 minutes. Then 516 g (50% purity) of the raw material combination solution (II) and the aqueous ammonium metatungstate solution were added, ). Further, 8.60 kg of powdered silica was dispersed in 77.4 kg of water and aged at 50 캜 for 1 hour as it was to obtain a raw material combination solution (III).

(Spray drying of the raw material combination liquid obtained in the combination tank)

Before the completion of the combination of the raw material combination liquid (III), hot air of 50 ° C adjusted to a feed rate of 80 kg / Hr and air heated to 210 ° C was supplied to the centrifugal spray dryer, Lt; / RTI >

The supply amount of the raw material combination liquid to be supplied to the spray dryer was adjusted so that the outlet temperature of the spray dryer was not changed, and the supply amount was 100 kg / Hr. In the meantime, the outlet temperature was 120 ± 5 ° C and there was no significant variation.

(Measurement of ultraviolet visible spectrum)

The obtained dried product was sampled every day, and 0.5 g of the obtained 10 sample products was measured by a diffuse reflection method in a range of 200 to 800 nm using JASCO UV / VIS Spectrometer V-650 manufactured by Nihon Bunko Co., Ltd. Spectralon manufactured by Labspere was used as a standard material for the baseline. The maximum absorbance was 1.02. The absorbance at 600 nm was 0.31 to 0.36, which was the absorbance with which high performance could be expected with reference to the description of JP-A-2009-148749. Therefore, the obtained spray dried product was used for classification operation without sorting.

(Classification operation)

The dried product thus obtained was classified using a sieve having a sieve size of 25 mu m to obtain a powder. The content of the particles of 25 mu m or less in the obtained powder was 0.8 mass% and the average particle diameter was 55 mu m.

(Firing of powder)

Seven slabs each having a height of 150 mm in a cylindrical sintered tube made of SUS having an inner diameter of 500 mm, a length of 3500 mm and a thickness of 20 mm were set so as to divide the length of the heating furnace into eight equal parts at a rate of 20 kg / hr And heated to 370 캜 for about 4 hours while rotating the fired tube at 4 rpm under a nitrogen gas flow of 600 N 터 l / min and heated to a heating furnace temperature of 370 캜 for 3 hours, And a shear fired product was obtained by shearing firing. Seven slabs each having a height of 150 mm in an SUS-made sintered pipe having an inner diameter of 500 mm, a length of 3500 mm and a thickness of 20 mm were installed so as to divide the length of the heating furnace into 8 equal parts. The sintering tube was rotated at 4 rpm , And shear debris was distributed at a rate of 15 kg / hr. At that time, with a hammering device provided with a hammer having a mass of 14 kg, which is made of stainless steel and the tip of the striking part was provided, was placed in the powder introduction side portion (the portion not covered with the heating furnace) The temperature profile was obtained by raising the temperature to 685 占 폚 at 2 占 폚 / min under nitrogen gas flow of 500 N / min while blowing once at 5 seconds from the height for 1 hour at 68 占 폚 for 2 hours, The temperature of the furnace was adjusted so that the oxide catalyst was obtained.

(Composition of oxide catalyst)

As a result of analyzing the composition of the oxide catalyst, the composition of the metal oxide was MoV _0.21 Nb _0.09 Sb _0.20 W _0.01 Ce _0.01 . The amount of silica supported was 47 mass% with respect to the total mass of the catalyst composed of the metal oxide and silica.

(Measurement of specific surface area)

As a result of measurement by the same method as in Example 1, the specific surface area was 15.1 m < 2 > / g.

(Removal of the stone body)

Was removed in the same manner as in Example 1.

(Total pore volume)

As a result of measurement by the same method as in Example 1, the total pore volume was 0.174 cm 3 / g.

(Pore distribution)

As a result, the ratio of the pore volume of pores having a pore diameter of less than 60 nm was 63.8%, and the ratio of pore volume of pores having a pore diameter of 120 nm or more was 0%.

(Average pore diameter)

As a result of measurement by the same method as in Example 1, the average pore diameter was 46 nm.

(Measurement of crystallite size)

As a result of measurement by the same method as in Example 1, the crystallite size was 98 nm.

(Ammoxidation reaction of propane)

Using the oxide catalyst obtained above, propane was provided for the vapor-phase ammoxidation reaction by the following method. A mixed gas of propane: ammonia: oxygen: helium = 1: 1: 3: 18 in a molar ratio of propane: ammonia: oxygen: helium = 1 was prepared under a reaction pressure of 440 ° C at a reaction temperature of 440 ° C. Contact time 2.8 (sec · g / cc). After the reaction, the conversion of propane was 90.1%, the yield of acrylonitrile was 53.1%, and the combustion rate of ammonia was 22.3%.

Table 1 below shows the composition and physical properties of the catalysts, the acrylonitrile yield and the ammonia burning rate in each of the examples and comparative examples.

The present application is based on Japanese Patent Application (Japanese Patent Application No. 2011-095422) filed on April 21, 2011, to the Japanese Intellectual Property Office, the contents of which are incorporated herein by reference.

The silica supported catalyst of the present invention has industrial applicability as a catalyst to be used in the production of the corresponding unsaturated nitrile by gas-phase contact ammoxidation reaction of propane or isobutane.

Claims (5)

A silica-supported catalyst for use in producing a corresponding unsaturated nitrile by vapor phase catalytic ammoxidation of propane or isobutane, which comprises a metal oxide represented by the following formula (1) and having an average pore diameter of 60 to 120 nm A silica supporting catalyst having a total pore volume of 0.15 cm 3 / g or more, a specific surface area of 5 to 25 m 2 / g and a crystallite size of 40 to 250 nm obtained from a half value width of a (001) peak by X-
MoV _a Nb _b X _c T _d Z _e O _n (1)
(In the formula (1), X represents at least one or more elements selected from Sb and Te, T represents at least one or more elements selected from Ti, W, Mn and Bi, and Z represents La, Ce, Yb And Y, wherein a, b, c, d and e each represent an integer of 0.05? A? 0.5, 0.01? B? 0.5, 0.001? C? 0.5, 0 <d? e &amp;le; 1, and n is a value satisfying the balance of valence valencies.) The method of claim 1, wherein the pore volume of the pores having a pore diameter of less than 60 nm is less than 30% of the total pore volume, and the pore volume of the pores having a pore diameter of more than 120 nm is less than 30% catalyst. The silica-supported catalyst according to claim 1 or 2, wherein the amount of silica supported is 20 to 70 mass% with respect to the total mass of the catalyst composed of the metal oxide and silica. A method for producing a silica-supported catalyst, comprising the following steps (I) to (IV);
(I) an atomic ratio a of V, a atomic ratio b of Nb, an atomic ratio c of X, an atomic ratio d of T, and a circle of Z containing Mo, V, Nb, X, T and Z, Y is 0, e <1, and 0 <e <1, respectively, wherein X is selected from Sb and Te Wherein T represents at least one or more elements selected from Ti, W, Mn and Bi, and Z represents at least one or more elements selected from La, Ce, Yb and Y fair,
(II) a step of drying the raw material combination solution to obtain a dry powder,
(III) a step of shearing the dried powder at 200 to 400 캜 to obtain a shear fired body,
(IV) a step of preliminarily firing the shear fired body at 600 to 750 ° C to obtain a fired body
(I) having an average primary particle diameter of from more than 0 to 30 mass% with respect to the total mass of the silica raw material of 3 nm or more and less than 20 nm, a silica sol (Ii) a silica sol having an average primary particle diameter of 20 nm or more and 100 nm or less of 70 mass% or less and a powdery silica having an average primary particle diameter of 50 nm or less in an amount of 30 to 70 mass% based on the total mass of the silica raw material, (i), the silica sol (ii) and the powder silica is 100% by mass based on silica. A process for producing a corresponding unsaturated nitrile by subjecting propane or isobutane to gas-phase contact ammoxidation reaction using the silica-supported catalyst according to any one of claims 1 to 6.